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Preface

widely used techniques to solve the eigenvalue problems of quantum-mechanical Hamiltonians. Its popularity is due to its simplicity and flexibility. The most crucial point in the variational approach is the choice of a variational trial function. One usually attempts to construct the trial function from some adequate basis functions which contain a number of nonlinear parameters. The direct method of diagonalizing the Hamiltonian matrix on such a basis set may not be feasible, except for simple systems, because of the large number of degrees of freedom involved in specifying the system. One thus faces a problem of selecting the most suitable basis set. It is by the stochastic variational method, that is, by a trial and error procedure with an admittance test that we give an answer to this problem. The stochastic variational method has been developed through the search for precise solutions of nuclear few-body problems. The variational method is

In this method

it enables

us

we

one

of the most

set up the basis element

to test many

parameters

to monitor the energy convergence. The aim of this book is to give

as

after the other because

one

fast

as

possible

and

moreover

unified and

reasonably simple problems with the use few-body recipe of the stochastic variational method and to present its application to various few-body problems which one encounters in atomic, molecular,

nuclear, subnuclear and solid

a

bound-state

for solutions of

state

physics.

quantum systems is in general extremely difficult and challenging, great advances have been made in recent years, especially for systems of a few particles and it has become possible to obtain accurate solutions for the eigenvalue prob-

Though

a

unified

approach

to the diverse

quantum-mechanical Hamiltonians. The main interest the few-body problems lies in, e.g., finding an accurate solution for

lem of various

in

the system

so as

to understand the

dynamics

of its

constituents,

test-

VI

Preface

ing the equation of motion and the conservation laws and symmetries, or looking for unknown interactions governing the system. Quantum mechanics plays a fundamental role in atomic and subatomic physics. It is via quantum mechanics that one can understand the binding mechanism of atoms, molecules and atomic nuclei, that is, the structure of the building blocks of matter. The interaction between the particles depends on the system: For example, the longrange Coulomb interaction dominates in atoms and molecules but the

very different mass ratio of the electrons and the atomic nucleus plays a key role as well. In contrast, the protons and neutrons in nuclei have

equal masses and the interaction between them is short-ranged. The variational foundation for the time-independent Schr5dinger equation provides a solid and arbitrarily improvable framework for the solution of diverse bound-state problems. As mentioned above, the most crucial point in the variational approach is the choice of the trial function. There are two widely applied strategies for this choice: One is to use the most appropriate functional form to describe the short-range as well as the long-range correlations among the particles. Such calculations, however, are fairly complex for systems of more than three particles, and the integration involved is performed by the Monte Carlo method. Another way is to approximate the solution as a combination of a number of simple basis states which facilitate the analytical calculation of matrix elements. We follow the latter course almost

in this book and show that the stochastic variational method selects

important basis set without any bias, keeps the dimension of and, most importantly, provides a very accurate solution. The book is conceptually divided into two parts. The first seven chapters present the basic concepts of the variational method and the formulation using Gaussian basis functions. The latter four chapters of the book cover applications of the formulation to various quantummechanical few-body bound-state problems. In Chap. 2 a general formulation is developed to express the physical operators which are needed to specify the Hamiltonian in terms of an arbitrary set of independent relative coordinates. The linear transformation of the relative coordinates induced by the permutation of identical particles is also established in this chapter. In Chap. 3 we review the basic principles of the variational method with particular emphasis on the case where the variational trial function is given as a linear combination of nonorthogonal basis functions. We introduce in Chap. 4 a key algothe most

the basis low

rithm used in this

book,

the stochastic variational

method,

and show

Preface

that its trial and

error

search

procedure

makes it

possible to

Vii

select the

important basis functions without any bias in the function space spanned by the basis functions. Some other methods to solve few-body most

briefly introduced in Chap. 5. Chapter 6 defines the type of variational trial functions used extensively in the book, the correlated Gaussians and the correlated Gaussian-type geminals. They are chosen because they enable us to evaluate matrix elements analytically and because they provide. us with precise solutions for most problems of real interest. A simple but powerful angular function is introduced to describe orbital motion with nonzero orbital angular momentum. To facilitate the systematic and unified evaluation of matrix elements,

problems

are

it is shown that the above Gaussian basis functions

function. In

7

are

all obtained

show that the

generatChap. deriving the matrix elements of the Gaussian basis functions for an N-body system of essentially any interaction. Explicit formulas axe given in this chapter for the simplest possible Gaussian basis functions, because they are already found to be very useful. The matrix elements for a, general case are detailed in the appendix. We show also in this chapter that the. method can be extended to evaluate the matrix elements of nonlocal potentials and the seniirelativistic kinetic energy as well. Chapters 8-11 present application of the stochastic variational method to various systems: small atoms and molecules (Chap. 8), baryon spectroscopy (Chap. 9), excitonic complexes and quantum dots in solid state physics (Chap. 10), and nuclear few-body problems (Chap. 11). We hope that this book will be found useful by students who want to understand and make use of the variational approach to quantummechanical few-body problems, while it may also be of interest to researchers who axe familiar with the subjects. It will be our pleasure if this book serves to bridge the gap between graduate lectures and the literature in scientific journals, as well as to give impetus to further development in the deeper understanding of quantum-mechanical fewbody systems. We assume that readers have taken courses on quantum mechanics and mathematical physics at an undergraduate level. No special knowledge is assumed of, e.g., atomic physics or nuclear physics. To help readers to understand the text, we have attempted to make the book self-contained, put as much emphasis as possible on clarity, and given several Complements of an explanatory nature. The Complements are intended to further develop or to reinforce the arguments and ideas presented in the text. We have collected the derivation

from

ing

a

generating plays a

function

vital role in

we

VIII

Preface

of formulas that may possibly be difficult for readers solutions at the end of the chapters.

as

exercises with

Depending on their interest, readers may adopt several reading strategies. A thorough-going reader is advised to read all of the text including the Complements. A reader who wants to understand only the basic formulation can omit the Complements. Anyone who is familiar with the variational method may skip Chaps. 2 and 3. Experts, or those readers who are only interested in the performance of the stochastic variational approach or the physical consequences of the results, may skip Chaps. 2-7. The Gaussian basis has long been used in many areas of physics. The correlated Gaussians were first introduced in quantum chemistry by S.F. Boys and K. Singer. The application of the Gaussian basis is one of the key elements of the success of the ab initio calculations in quantum chemistry. The stochastic variational method is actually very similar to the so-called "random tempering", that has been used to find the optimal parameters of the basis in quantum chemistry. In the random tempering pseudo-random parameters axe generated, and the best basis functions are selected by sorting out the states which improve the energy. There exists another method which is also similar to the stochastic variational method, called the stochastic diagonalization. This method, originally developed in solid state physics, attempts to find the lowest eigenvalue of huge eigenvalue problems by randomly testing the contributions of different states. The random selection of the parameters of a Gaussian basis, named the stochastic variational method, was first used by V.I. Kukulin and V.M. Krasnopol'sky in nuclear physics. We are grateful to Prof, V.I. Kukulin for his interest and encouragement during this work. We are indebted to our collaborators, K. Arai, Y. FujiNvara, L.Ya. Glozman, R.G. Lovas, J. Afitroy, C. Nakamoto, H. Nemura, Y. 0hbayasi, Z. Papp, W. Plessas, G.G. Ryzhikh, N. Tanaka, J. Usukura, and R.F. Wagenbrunn for useful discussions and for many of the calculations which press

our

hearty

are

included in this book. We wish to

thanks to Prof. K.T.

Hecht,

ex-

Prof. D.

Baye, Prof. reading of the Despite all these

M. Kamimura and Prof. R.G. Lovas for their careful

manuscript and for much advice and many comments.

efforts mistakes may still remain. Needless to say, these are our own responsibility. Suggestions and criticisms from our readers would be welcomed. We

are

grateful

for the

use

of the computer VPP500 of (RIKEN). One of the

the Institute of Physical and Chemical Research

Preface

for the

authors

(K.V.)

ment of

Niigata University and

is

grateful

would like to thank the

Research of the

hospitality

the Linac

funding agencies,

Iffinistry

of

(Hu gary),

of the

Ix

Physics Depart-

Laboratory

of RIKEN. We

Grants-in-Aid for Scientific

Education, Science and Culture (Japan),

Japan Society for the Promotion of Science (JSPS), the Science and Technology Agency (STA) of Japan, the U. S. Department of Energy, Nucleax Physics Division, and the Hungarian Academy of Sciences (HAS), for their support which has been vital for the completion of the work. Finally, without the support and patience of our families, this book would not have been possible. OTKA Grants

Niigata Argonne September

the

Y. Suzuki K.

1998

Varga

Table of Contents

I..

Introduction

2.

Quantum-mechanical few-body problems

........................................

...........

7

2.1

Hamiltonian ......................................

7

2.2

Relative coordinates

..............................

9

..................................

15

2.3

Symmetrization

2.4

Permutation of the Jacobi coordinates

Complements C2.1 An N-particle Hamiltonian in the heavy-particle center

..............

.........................................

Variational

3.2

The variance of local energy The virial theorem

3.3 4.

principles

......................

19

4.2

21

21

.......................

30

................................

33

.......................

39

................................

39

...............................

43

......................

44

.........................

47

..............................

47

....................................

50

Basis

optimization A practical example 4.2.1 Geometric progression 4.2.2 Random tempering 4.2.3

Random basis

4.2.4

Sorting

4.2.5

Trial and

error

search

.......................

Refining 4.2.7 Comparison of different optimizing strategies Optimization for excited states

4.2.6

4.3

................

.............................

Stochastic variational method 4.1

18

18

Introduction to variational methods 3.1

16

...........

coordinate set

C2.2 Canonical Jacobi coordinates 3.

1

...................................

.................

50 53

.

54

....

56

.

I

Complements

.........................................

61

XII

Table of Contents

C4.1 Minimization of energy 5.

versus

variance

..............

Other methods to solve

5.2

few-body problems Quantum Monte Carlo method: The imaginary-time evolution of a system Hyperspherical harmonics expansion method

5.3

Faddeev method

5.4

The generator coordinate method

5.1

.........

...........

6.

..................................

Variational trial functions 6.1

6.2

6.4

65

67 70

72

..........................

75

Correlated Gaussians

Gaussian-type gerninals Orbital functions with arbitrary angular Generating function The spin function

Complements

..............

.

82

87

................................

94

C6.2 Solid

spherical harmonics C6.3 Angular momentum recoupling C6.4 Separation of the center-of-mass =

as a

basis

.....

96 96 105

.....................

106

motion

.........................

1/2

......................

arbitrary spin arrangement

112

115

......

115

...........................

116

............................................

118

an

C6.7 Six electrons with S

Matrix elements for

=

0

spherical Gaussians, generating function

............

123

..........

123

..............................

125

7.1

Matrix elements of the

7.2

Correlated Gaussians

7.3 7.4

Correlated Gaussians in two-dimensional systems Correlated Gaussian-type gendnals

7.5

Nonlocal

7.6

Semirelativistic kinetic energy

Complements

potentials

.

129

.................

131

.

.

.

.

...............................

......................

.........................................

C7.1 Sherman-Morrison formula Exercises

.

..........................

from correlated Gaussians

C6.5 Three electrons with S

Exercises

momentum

.........................................

C6.6 Four electrons in

75

..............................

C6.1 Nodeless harmonicoscillator functions

7.

65

...................

and correlated

6.3

.........

61

134 137

143

........................

143

............................................

145

Table of Contents

8.

Small atoms and molecules

.........................

8.3

Coulombic systems Coulombic three-body systems Four or more particles

8.4

Small molecules

8.1

8.2

.......

149

.....................

150

...................................

.........................................

C8.1 The cusp condition for the Coulomb potential C8.2 The chemical bond: The H,+ ion C8.4 9.

Stability hydrogen-like Application of global vectors

169

.................

to muonic, molecules

174

................................

177

One-gluon exchange model Meson-exchange model

.....

178 178

............................

181

quark

...........

188

...................................

191

....................

196

method

a

magnetic

204

..........................

213

...

213

.............

216

...............................

223

.........................................

230

11.2 Few-nucleon

systems with central forces

potentials

C11.1 Correlations in few-nucleon systems C11.2 Convergence of partial-wave expansions Pauli effect in s-shell A

C11.4 The "C nucleus

Appendix

202

field. 204

few-body systems Introductory remark on nucleon-nucleon potentials

Quark

....

.........................................

11. Nuclear

C11.3

187

..............................

C10.1 Two-dimensional electron motion in

as a

...............

230

............

233

..........

239

.

242

hypernuclei system of three alpha-particles

...............................................

Matrix elements for

A.1

model

........................

Few-body problems in solid state physics 10.1 Excitonic complexes 10.2 Quantum dots 10.3 Quantum dots in magnetic field 10.4 Quantum dots in the generator coordinate

Complements

171

....

9.2

11.3 Realistic

167

....................

The trial function in the constituent

11. 1

165

167

9.1

Complements

154

........

molecules

Baryon spectroscoPy

9.3

10.

of

149

........................

............................

Complements

C8.3

XIII

general

Correlated Gaussians

A. 1. 1

Overlap

A.1.2

Kinetic energy

Gaussians

..................

.............................

of the basis functions

247 247

247

................

247

.............................

249

Table of Contents

XIV

A.1.3 A.1.4

......................

250

..................

256

Two-body interactions Density multipole operators

A.2

Correlated Gaussians with different coordinate sets

A-3

Correlated

matrix elements

Spin

A.5

Three-body problem and spin-orbit forces

Complements

.................

262 263

with

central,

tensor

..............................

265

.........................................

280

CA. 1 Matrix elements of central potentials CA.2 Matrix elements of density multipoles

CA.3

...............

280

..............

283

matrix elements of the correlated Gaussians

Overlap a three-particle system

for

Exercises

References Index

257

.............................

Gaussian-type geminals

AA

...

.........................

285

............................................

288

..............................................

...................................................

299

307

1. Introduction

There

are a

countless number of examples of quantum-mechanical few-

body systems:

constituent

quarks

in subnuclear

physics, few-nucleon

few-cluster systems in nuclear physics, small atoms and molecules physics or few-electron quantum dots in solid state physics, etc. The intricate feature of the few-body systems is that they develop or

in atomic

depending on the number of constituent particles. The mesons and baryons, the alpha-particle and the 'Li nucleus, or the He atom and the Be atom have very different physical properties. The most important causes of these differences are the correlated motion and the Pauli principle. This individuality requires specific methods for the solution of the few-body Schr6dinger equation. Approximate solutions which assume restricted model spaces, mean field, etc. fail to describe the behavior of the few-body systems. The goal of this book is to show how to find the energy and the wave function of any few-particle system in a simple, unified approach. The system will normally be in the minimum energy quantum state. As forewarned, however, to find this state, the ground state, is a complicated matter. The present stage of the development of computer technology, however, makes a very simple approach possible: Searching for the ground state by "gambling". Without any a priori information on the true ground state, completely random states are generated. Provided that the random states axe general enough, after a series of trials one finds the ground state in a good approximation. The reader individual characters

may find this

a

little

suspicious but there are indeed a number of fine error procedure which makes the whole idea

tricks in the trial and

really practicable. Before bombarding the

reader with

sophisticated details, let us example. Let us try to determine the energy of a Coulombic three-body system: a positron and two electrons, the positronium negative ion, Ps-. The example is simdemonstrate the random search with

Y. Suzuki and K. Varga: LNPm 54, pp. 1 - 6, 1998 © Springer-Verlag Berlin Heidelberg 1998

an

1. Introduction

2

ple enough so t1i at a graphic illustration of the wave function can be given, but its solution is far from being trivial. The ground state of this particular system can be calculated by different methods accurately. In the rest of this chapter we will give just the outline of the gambling method without paying much attention to the details. To look for the wave function of the ground state of the system, we generate random functions. The functions we assume some

continuous a.re

parameters

or

randomly

chosen. For

Tf (a, 0, x,

y)

=

=

are

random in the

depends

on some

sense

that

discrete

or

"quantum numbers" and these paxameters example, we assume a simple Gaussian form

e`2 -

3Y2

(1.1)

7

1r2 -7'31 denotes the distance between the two electrons and I (r2 +r3) /2 r 1 1 denotes the distance between the center-of-mass

where Y

functional form which

x

=

-

of the electrons and the

positron.

randomly chosen generated states are calculated and compared. The one among them giving the lowest value is selected to be a successful paxameter set. Figures 1.1(a)-(d) show examples of four random states and their energy expectation values which are obtained with such successful paxameters. Not surprisingly, the energies of the "configurations" appreciably depend on the shape of the functions, that is, on the random paxameters. The lowest energy, -0.11 in atomic units (a.u.) in Fig. 1.1(d), is higher than that of the exact ground state (-0.262). Here in the atomic units M, (the electron mass), e (the electron charge magnitude), and h axe chosen to be basic quantities of units, so the unit of length is Bohr radius h?/(Mee2) 5.29x1O-11 m, theunit of energyis me4/h? 27.2 ao 2.42 x 10-17 S. (Actually the and the unit of time is h3/(me4) eV, minimum energy calculated analytically with one term of Eq. (1.1) is -0.177, but it may not be known for a general case.) That means that the trial function is not general enough to describe the ground state. To improve the trial function, let us take a linear combination of two of the above functions of Eq. (1.1), where one of the two is fixed as the one already selected and another is newly selected after a number of random trials. Figures 1.2(a)-(d) show examples for random wave functions which are calculated by the two terms. The energy improved because the model space increased but we still miss a substantial amount of binding energy. Increasing the model space further A certain number of parameter sets a and and then the energy expectation values of the

=

axe

=

-

=

by adding one,

we

more

and

more

functions to the linear combination

reach the exact energy and the

wave

function

one

(Fig. 1.3)

by

with

1. Introduction

E--0.09

E--3.15

E=0.18

E--0.11

Examples of the energy expectation value and the (normalized) xyTf (a, 3, x, y) of Ps- for one random basis state. Figure 1(a) is in the upper left, 1(b) in the upper right, 1(c) in the lower left, and 1(d) in the lower right. In each section the x axis denotes the distance

Fig.

wave

1-1.

function

between the two electrons and the y axis denotes the distance between the center-of-mass of the two electrons and the positron. Atomic units are used.

1. Introduction

E-0.14 E=-0.18

0.1

0.0

B-0.12 E=-0.17

0.1 0.0

Fig.

1.2.

Examples

xyjcj-T1(aj, Oj

of the energy expectation value and the

wave

function,

y) +c2Tf(a2, 02 Xi Y) ji of Ps- for combinations of two random. basis states. Figure 2(a) is in the upper left, 2(b) in the upper right, 2(c) in the lower left, and 2(d) in the lower right. See also the caption of -,

Fig.

1. 1.

x,

1

1. Introduction

a

combination of about 150 functions of the form

(1.1).

The

5

conver-

gence of the energy versus the number of the functions in the linear combination is shown in Fig. 1.4. The energy gain is large in the first

few steps and then it

slowly approaches the

exact energy.

E=-0.262

X

Fig. and

1.3. The energy and the wave function of Ps- obtained selection of 150 basis states

by the trial

error

The alert reader may question the importance of the steps that are taken to increase the model space and can ask why not start say, a linear combination of 150 functions and then, by random of all the parameters, one may find the solution. The reason for trials

with,

increasing the number of functions in the combinations is to control "convergence" of the energy. By comparing the energy gain in the successive steps one can guess how far the exact ground-state energy the

is. There is

no

guarantee that the ad hoe 150 functions would be

1. Introduction

6

-0.250

-0.252 M 41

-0.254

-0-256

-0.258 Z

-0.260

-0.262 20

40

60

80

100

Dimension of the basis

Fig.

1.4. The energy convergence of Ps- as a function of dimension of basis are increased one by one with the trial and error selection. The

states that

solid, dashed and dotted

curves

correspond to

sufficient to reach the solution in

cases

three different random

paths.

where the exact energy is not

known. A

skeptic may say that one should, instead of the above gambling method, try a deterministic parameter search such as that furnished by the Newton or conjugate gradient method. While this may be true for small systems, the random trials the

axe more

successful in most of i

in the

I

a. by avoiding being trapped omnipresent local Moreover, one may have discrete paxameters or quantum numbers

cases

where the deterministic seaxch may not be suitable. One may also wonder if the solution we reach is the in

ground state energy. These the succeeding chapters.

and other

really (close to)

questions will be answered

Quantum-mechanical few-body problems 2.

first step toward the goal of giving a unified and reasonably simple recipe for solutions of few-body bound-state problems the basic

As

a

notations and concepts

The motion of the ton

operator

axe

introduced here.

few-body system

(Hamiltonian)

and described

governed by the Hamilby the eigenfunction of the

is

depends on the positions and other degrees of freedom of the particles. See, for example, [1, 21 for textbooks on quantum mechanics. One can define the positions of the particles in several different ways by using single-particle or relative coordinates. The single-particle coordinates are useful if the particles move ah-nost independently of each other. The relative coordinates are advantageous to emphasize correlations between the particles and Hamiltonian. This

to

wave

function

separate the center-of-mass motion. One

can

relate the different

coordinate systems to each other by linear transformations. The definitions and the properties of these transformations are elaborated in this

chapter.

indistinguishable particles. To comply with the Pauli principle the wave function has to be properly symmetrized. In the spatial paxt of the wave function the symmetrization induces permutations of the coordinates. It is shown that these permutations can be imposed by linear transformations in the relative coordinate One often deals with

space.

2.1 Hamiltonian isolated system of N particles with masses ml., and let 7,1,, ,,rN denote the position vectors of the particles. -, mAT All of the particles may be identical or different, or some group(s) of them may be identical. The Hamiltonian of the system, with the

Let

us

consider

an

*

center-of-mass kinetic energy Tcm

being subtracted,

Y. Suzuki and K. Varga: LNPm 54, pp. 7 - 20, 1998 © Springer-Verlag Berlin Heidelberg 1998

reads

as

Quantum-mechanical few-body problems

2.

8

N

N

2

H=E 2mi

-T,.

As the interaction

(2.1)

Vij.

+

unchanged by the displacement of the origin, the above Hamiltonian is translationaUy invariant and depends on the internal degrees of freedom only. One may encounter few-body, problems where the system is subjected to some external field or the particles move in a single-particle potential. The Hamiltonian then reads as IV

H

=

N

2

E2

remains

Vij

+

1: Ui + 1: i=1

i=1

N

(2.2)

Vij.

i>i=l

Even with the presence of the one-body potential Ui it may happen that one wants to remove the contribution from the center-of-mass motion. This will be considered later in

evaluating the matrix elements

of various operators. An extension of the nonrelativistic kinetic energy to the relativistic kinematics will be discussed in Sect. 7.6.

Three-body potentials can be treated in principle but axe suppressed for the sake of simplicity. The two-body potentials are assumed to be local (but nonlocal potentials will also be considered in Sect. 7.5) and can in general be expressed as

Vij

=

1: VP(ri

-

rj) 0?.

P

=

1: f VP (r) J(ri

-

rj

-

r) 0?. dr.

(2.3)

P

Here p is the short-hand notation to specify the component of the potential which is characterized by 0?. (e.g., central, spin-orbit, etc.

and

VP(r)

is the

corresponding form factor.

To

specify

the

particle

motion, several degrees of freedom are in general needed besides the spatial one. For example, the nucleon has spin and isospin degrees

freedom, and the quark has spin, flavor and color degrees of fre&dom. The specific potentials related to nuclear, subnuclear and other of

systems will be discussed in later sections.

2.2 Relative coordinates

9

2.2 RelatiVe coordinates The

separation of the center-of-mass motion

care

of most

is

important to describe intrinsic excitations of the system. The center-of-mass motion is taken mass

conveniently by introducing

coordinates;i

(XIi X2

relative and the center-of-

xN). The symbol- stands for a trans-

pose of a matrix. In particular, x is often used to stand for one-column matrix whose-ith element is xi, whereas ,'c a I row

an

x

N

IV

x

1

one-

matrix. Here XN is chosen to be the center-of-mass coordinate of

the system and the rest of the coordinates

relative coordinates.

independent single-paxtide coordinates

i

-=-

They

(rj,

-'

fXI,

axe

in

-

-

-,

X N-I

general

I

is

a

set of

related to the

TN) by a linear transformation:

N

Uijrj,

xi

ri

=

j=1

E (U-I)ijxj

(i

N).

(2.4)

j=1

We show two

examples

of relative coordinates

is the Jacobi coordinate set, which is defined

by

x.

See

Fig.

2. 1. One

the matrix

C

2

4 3

0

0

(a) Fig.

2.1.

Examples

(b)

of relative coordinates for the

four-particle systein. (a)

the Jacobi coordinate set, xi =rl -r2, X2:-- (MIrI +M2P2)/(MI +M2)'r3 7 X3 = (Tnlrl + M2r2 + M3 r3)/(Ml + M2 + M3) -P47 and (b) the heavyparticle center coordinate set, xi = rl r47 X2 = r2 r47 X3 = r3 r4-

-

-

2.

10

Quantum-mechanical few-body problems 1

-1

MI

M2

M12

M12

M1

M2

0

0

...

0

(2.5)

Ui M12

...

M12

N-I

...

N-I

M1

M2

Tal2---IV

Tnl2---.LV

MN ...

...

M12

...

N

given by

Its inverse matrix is

M2

M3

M12

M123

MIV ...

Tni

M3

M12

M123

M12

---

M

MN ...

(Uj)

M12

...

N

(2.6)

M 12

0

M123

-"M12

0

0

...

N-1

M12 ...N

where M12 i +mi and, especially, 7nl2---N is the total Tnl+Tn2+ the "heavy-particle center" coordinate is Another the of mass system. -

...

set defined

UC

by 1

0

0

0

1

0

-1 -1

...

(2.7)

-

0

0 M12

---

N

...

-1

...

MN

M2

Mj_

...

...

M12

...

given by

and its inverse matrix is

...

N

M12

...

M

N

(UC )-I

M12

...

M12

...

N

M1V-I

M2

MI ...

MN-I

M2

M, M12

M12

M12 ---N

M

N

M12

N

M2

M12

...

N

MN-I

M2

MI

M12

...

N

M12

...

N

M12

...

N

(2.8) The choice of the when the other

mass

particles.

heavy-particle

See

center coordinates may be natural

particle is heavier than the masses of the Complement 2.1. Note, however, that it is always

of the Nth

2.2 Relative coordinates

11

possible to transform from one coordinate set to another. The Jacobian corresponding to the coordinate transformation (2.4) is unity for both U matrices.

Corresponding to the transformation (2.4), the momentum pi is -ih ya conjugate to the expressed in terms of the momentum -xj axj =

coordinate xj: IV =

Pi

N

1: Ujilrp

Wi

=

1:(U-l)jipj

(i

=

1,

...,

N).

(2.9)

j=1

j=1 N

Note that -7rAT

=

Ej=1 p,

is the total momentum. The center-of-mass

kinetic energy is given by T,,n ir2,v/(2MI2 N). The kinetic energy with the center-of-mass kinetic energy subtracted is then operator =

...

expressed

as

P

(27ni 6ij

2mi

i=1

i=1

2m12

...

N)

Pi

Pj

j=1

M-1 N-I

Aij-xi

2 i=1

-

(2.10)

-7rj,

j=1

where N

1: UikUjk Mk

Aij

(i,j

=

11

....

N

-

1).

(2.11)

k=1

To evaluate the potential energy matrix elements for the tions that contain

no

dependence

on

the center-of-mass

wave

func-

coordinate,

it

is convenient to express the single-particle coordinate relative to the center-of-mass, ri xN, the interparticle-distance vector, ri -,rj, and -

difference, pi pp in terms of x and easily done by using Eqs. (2.4) and (2.9):

the momentum This is

-

-x,

respectively.

1V-1

ri

-

XN

=

1: (U-l)ikXk

-W X,

(2.12)

k=1 N-I

'ri

-

r3

1: k=1

((U-l)ik (U-I)jk) -

Xk

=

W(j) X,

(2.13)

Quantum-mechanical few-body problems

2.

12

N-1

2

(Pi

Pj

E (Uki

2

-

(ij )Ir-

Ukj)7rk

(2.14)

k=1

Note that the contribution from the term

momentum,

(Mi

is

when

legitimate

-

Mj)/(2Ml2 N)7rN, ...

we are

proportional to the total omitted in Eq. (2.14). This

is

in the center-of-mass

(,7rlV

system

=

0)

and

interested in the intrinsic motion of the system. The Hamiltonian of type (2.1) is now expressible in terms of independent relative coordinates alone. In what follows

and

x

7r are

relative coordinates unless otherwise

(i.e. (N

introduced to

the notation.

by the

W(i) EN-I k Xkk=1

=

they are (N-1) x 1

stated,

-

1)

1 one-column

x

I)-dimensional vectors) 0), Oj),

simplify

which is formed

-W X

-

represent only the

that

so

Eqs. (2.12)-(2.14), (N

one-column matrices. In matrices

meant to

Wx

E.g.,

is

a

and

(W)

are

Caitesian vector

multiplication of iv(i) and x, i.e., that Oj) and (W) satisfy the following

usual matrix Note

equalities M-1

-((ij)

3 W(ij) (k k

W( ij

=

(-ipw(ij)

k=1 N

W(ij)(1(ij)

W

k

i>i=l

(ij)

F(ij)

i>i=l

kI

N

where the relations UNTj

for k

=7 -

For

N

are

an

(N

-

1) x (N

-

1) symmetric

scalar

products

E xi-(Ax)i with this

i=1

=

1,

EN

Uki

=

0

A,

let the

quadratic

of the Cartesian vectors:

xv)

j=1

convention, that

1V -

matrix

Aijxi-xj. i=1

show,

ai(ri

(2.15)

N-1 N-1

i=1

It is easy to

1),

?ni/?nl2---N, (U-1-)iN

=

N-I =

-

used.

form, bAx, represent

..bAx

N

R, I

Jk, 2

2

i=1

ajw(')J))

x,

(2.16)

2.2 Relative coordinates N

1V

I:

a

(ri _,rj)2

ij

1:

=.i

a

ajjw

-(ij)

(ij)

(2.17)

X.

i>i=l

i>i=l

As

13

special case of the above relations, we have the following equalities

for the moment of inertia around the center-of-mass: N-1

N

N

Mi(ri

-

XN

MzMj

)2

M12

where the reduced is defined

mass

...

N(ri

Tj)

-

corresponding to

ILi

2

(2.18)

the Jacobi coordinate xi

by ?ni+17nl2 M12

...

z

...

(2.19)

1).

N

i+1

We also obtain 2

N

N

(ri

-

T'j )2

N

=

E(ri XN)2

(,ri

_

-

(2.20)

xiv)

i=1

The term are

the

E , (ri

-

XN)

masses

of all the

particles

same.

The total orbital mass

vanishes when the

system

(-xv

=

angular

0)

momentum

be

can

operator L in the center-of-

expressed

in terms of the

operators

relevant to the relative coordinates: N-1

N

hL

(ri

((,ri

-

X

Pj)

Tj)

(XN

X

2

(Pi

X

-

(Xi

7N)

X

7ri),

(2.21)

Pj))

i>i=l N

or i

-

X

'r

Rij)

-X

i>i=l

+

((ri

-

W('j)X

rj) XMi

-

2M12

X

Mj 7rN ...

N

(('j)-7r) =NU. 2

(2.22)

Quantum-mechanical few-body problems

2.

14

Eq. (2.22) use is made of Eq. (2.15) in the last step. Thus the equality of Eq. (2.22) holds in the case one considers the orbital angular 0 or treats a system of paxticles momentum in the system of 7rjV with equal masses. In atomic physics the trial function of Hylleraas type or correlated In

=

exponential type is often used with success. This function contains the exponential form expressed in terms of the interparticle-distance coordinates. T-nstead of the exponential function let us consider its Gaussian analogue IV

T

=

exp

E

2

aij (ri

-

rj )2

(2.23)

i>i=l

aij determine the falloff of the interparticle functions and may be considered variational parameters. Since not all of the N(N 1)/2 interparticle-distance vectors, ri rj, are Here

N(N

1)/2 parameters

-

-

-

(Irl T2) + (T2 -r3), it is convenient to T3 e.g., TI rewrite T in terms of the independent coordinates x. This is needed to independent,

calculate, e.g., the Eq. (2.23) as T

=

exp

aij

are

-1

(

(N

where the

=

-

-

2 -

related

1)

norm

-

of T.

Equation (2.17) enables

one

to rewrite

iAx), x

(N

-

(2.24)

1) symmetric matrix A

and the parameters

by N

N

-

(ij)

AkI

ajjWk

(ij) WI

=

I:

aij

(W

(ij) W(ij)

) kl'

i>i=l

i>i=l N-I N-1

aij

-

1: 1: UkjAkIU1j k=1

=-

-(CTAU)ij

(i

(2.25)

<

1=1

By substituting Akj of the first relation to the second relation one can check the validity of the second relation. The above two forms,

(2.23)

and

(2.24),

are

thus

equivalent.

We introduce both because in

applications the first form or in some others the second form is more advantageous. See Complements 6.4 and 7. 1. The norm (Tf I Tf) becomes finite if and only if A is positive-definite and is then given by some

((270N-1 /detA)

I 2

-with the

use

of

Eq. (6.32)

or

A necessary and sufficient condition of the a

symmetric

Exercise 6.2.

positive-definiteness

matrix A is that the matrix A is

expressible

as

A

of =

2.3

dDG,

where G is

an

(N

1)

-

x

(N

Symmetrization

1) orthogonal matrix containing is a diagonal matrix, Dij diJij,

-

1) (N 2) /2 parameterg and D including (N 1) positive parameters di. (N

-

15

-

=

-

closing this section, we remark that the matrix Uj of Eq. orthogonal in general. In some cases it is convenient to use a (2.5) coordinate system that is obtained from the single-particle coordinates by an orthogonal matrix. We show such an example in Complement Before

is not

2.2.

Symmetrization

2.3

function of the system must have a proper symmetry for the interchange of identical particles. This is achieved by operating on the The

wave

basis function with for bosons

or

the

suitable operator P, which is the symmetrizer antisymmetrizer for fermions. The operator P can in a

general be given by a combination of the permutations P with suitable 1

phases. The permutation transforms the Pr

=

P

=

(PI

2

'V

P2

PN

single-particle coordinates

as

ri

)

-+

of paxticle indices

rp,:

(2.26)

Tpr,

where the matrix Tp is

(Tp) ij E.g.,

=

(i, j

Jj pi

the matrices

Tp

are

1

0

0

0

1

0

T123

1,

=

...'

given as follows

1

(321

T123

(

The

T123

(2.27) in the

case

of three

0

1

0

1

0

0

0

0

1

0

particles:

213

123

T123'

N).

0

0

0

0

1

0

1

0

1

0

0

1

0

0

1

1

0

0

on

the

1

1

0

0

0

1

0

0

1

0

0

0

0

1

1

0

0

0

1

0

T123 132

T123

(3121

23 1

operation of P

wave

it is written in terms of the

function is thus not

(2.28)

a

single-particle coordinates.

problem

when

Quantum-mechanical few-body problems

2.

16

When the

ordinates,

wave

have to note

we

expressed in terms of the relative cothat the permutation P induces a lineaX

function is

transformation of the relative coordinates Px

=

follows:

as

(2.29)

Tpx,

by using Eqs. (2.4), (2.26) given by

where

(2.27)

and

the matrix Tp is

now

N

(TP)ij

1: Uik(U-1)Pki

(i,j

=

'I

...

I

N

-

1).

(2.30)

k=1

Though

we use

matrix is

which is

now

the

same

notation of

(N 1) x (N 1) -

-

Tp,

note that the size of the

because the center-of-mass

coordinate,

unchanged under the permutation, is eliminated. We Will show

Chap. 6 that the properties of Eqs. (2.26)-(2.30) can be used advantage for Gaussian functions. See Eqs. (6.28) and (6.29).

in

to

2.4 Permutation of the Jacobi coordinates

generate different sets of Jacobi coordinates by interchanging the paxticle labels by permutations. Figure 2.2 shows an example of One

can

three different sets,

x('), X(2)

,

and

X(3),

of the Jacobi coordinates for

three-body system. These sets are completely equivalent from the point of view of the dynamical description of the system, but they can be advantageously used in the calculation of the matrix elements. In the Jacobi coordinate set, defined by Eq. (2.5), the first Jacobi coordinate is equal to I'l -r2. By permutations one can create other Jacobi coordinate sets X(k) where the first Jacobi coordinate takes a

rj. The index k refers to the kth permutation and distinguish the permuted Jacobi coordinate set. As the two-

the form of ri serves

to

-

body potential depends on this coordinate, the set created by the permutation will prove to be useful. See Appendix A.5 for an example of using the permuted Jacobi coordinate set. Another peculiarity of the Jacobi coordinates is that if we are in the center-of-mass system (-xiv 0) then by using Eqs. (2.5) and (2.9) --xiv-11 that is, one of the single-paxticle momenta is equal to p1V the relative momenta. By permutations we can express any of one of the single-paxticle momenta in terms of a certain momentum of =

=

the relative momenta. This

simple expression can be exploited in sevevaluating matrix elements of operators

eral ways, because instead of

2.4 Permutation of the Jacobi coordinates

a-

is

*+-3

Mw-

2

3

Ak

a&-

71

IRW

Ah MW

1

2

3

2

2.2. Different sets of the Jacobi coordinates for the

Fig.

tem. From left to

right: x(l), X(2),

containing single-particle an

application

we can

do

so

See Sect. 7.6 for

versa.

three-particle sys-

x(3), respectively.

and

momentum

relative momentum and vice

17

with operators of more details and

to the calculation of matrix elements for the semirela-

tivistic kinetic energy. The permutation of the Jacobi coordinates is defined

by the corresponding cyclic permutation

of the column vectors of Uj and the

permutation exchange of the

(1, 2, the

...,

N)

=

For

masses.

1

(2

2

example, for

N)

3

the

the transformation matrix between

1

singlt-,particle coordinates

r

and the Jacobi coordinates

x(f)

takes

the form 0

1

-1

0

M2

M3

M23

M23

0 ...

0

U(k)

(2.31) M2

-1

MAF

M3 ...

M23

...

M

M23---.LV

N

M12

M2

MI

M23---N

MN

M3 ...

M12---N

M12

...

...

N

M12

---

N

The relative coordinates in the different Jacobi coordinate sets

expressed by

X(k)

=

each other

T(k) X

through

T(k)

=

can

be

the transformation:

UMU-1. i

(2-32)

symmetrization in Sect. 2.3 and the permutation of the Jacobi are formally very similar. The main difference is that while the symmetrization is assumed for identical (and therefore equal mass) particles, in the latter case we allow for particles with different masses. The

coordinates

Complements

18

Complements 2.1 An

N-particle

Hamiltonian in the

heavy-particle

center coordinate

set

that the

Suppose

mass

of

of the

one

particles,

say the Nth

paxticle,

is the heaviest among all the paxticles. In this case the choice of the heavy-paxticle center coordinate may be natural paxticularly when the

position of the Nth paxticle is close to the center-of-mass of the system, like in an atom, where the Nth particle is a nucleus. The Hamiltonian (2.1) can be reduced to the form which contains no explicit dependence the variables of the Nth

on

is

particle.

By using Eqs. (2.7), (2.10) and (2.11) the Idnetic energy operator expressed in the heavy-paxticle center coordinates as N

N-I N-I

2

1

,

P7

E 2mi

-

T.-

=

EE i=1

i=1

( 2mi k 2mjV) +

-

I-ii .7rj

j=1

N-1

1: i=1

N-1

70z

1 +

2jLjjV

-

TaN

E

(2-33)

Iri .7rj,

j>i=l

'where jLjN mimN/(Tni + Talv) is the reduced mass for the ith and Nth particles. The potential energy VjV (i 1, ..., N 1) is a function =

=

of ri -rN on

xi and

=

the ith

can

be considered the one-body potential Uj

On the other hand the

particle. lighter particles can

N-I

H=E i=1

Potential

energy

function of ri -,rj xi thus be reduced to the type of Eq. (2.2)

between the

HamiltoTdan

-

2AjN

=

a

-

xj. The

N-1

N-I

2

^7r'

is

acting Vij acting

+EUi+ 1:

(Vij+

MN

7ri-7rj).

(2-34)

j>i=i

=1

problem is thus reduced to that of an (N-1)-paxticle system with an external field Uj and an additional separable "two-body potential"

The

oo, jLjjv goes to mi and the 7ri .7rj term The effect of the finite nucleax mass in the helium atom

7ri -7rj. In the limit of m1V -

disappears. was

discussed in

-->

[3].

The above formulation

can

also be

applied

to

a

system of identi-

particles when some, or most, of them form an inert core. As an example let us take up the nuclear shell model, where the nucleons

cal

are

divided into two groups, the passive or inactive nucleons and a small number of active nucleons. The passive nucleons form

relatively

C2.2 Canonical Jacobi coordinates

19

by filling the lowest possible single-particle orbits and exert a potential field Ui on each of the active nucleons. The active nucleons may occupy several single-particle orbits belonging to several major shells outside the inert core. In this approximation it is desiran

inert

core

able to describe the motion of the active nucleons without inclusion

arising from the center-of-mass motion. It is clear can be excluded by taking the full Hamiltonian have the form (2.34) with the core as the heavy particle.

of any excitations

that such excitations to

2.2 Canonical Jacobi coordinates

As

was

2.2, the Jacobi coordinates

noted in Sect.

that the transformation matrix Ui of Eq.

is,

neither

following

UjUi-

nor

relations

UjA-'Uj

Uj-Uj

equal

(2.5)

have the property orthogonal, that

to the unit matrix.

Instead, the

fulfilled:

are

L-1,

=

is

x

is not

UiLUi

=

(2.35)

A,

with

Aij

Jij

Lij

(2.36)

Jij, Ai

Mi

N where pi (i 1, 1) is the reduced mass belonging to the ith Jacobi coordinate and is defined in Eq. (2.19), while 1LV is equal to the =

-

the transformation between

the singleUir and p UT-x, of paxticle and the Jacobi coordinate systems, x identities the lead above relations the to and following (2.9), Eqs. (2.4) total

mass

'MI-2

N.

...

By using

=

N

N

E Tnir?

=

z

N

E Nx

Alternatively,

N

pi2

E

-

Mi

one can

introduce

Ir2i

=

-(2.37)

Ai

"canonical" set of Jacobi

a

coor-

dinates: IV

Vijrj

with

V

=

A

2

UiL 2.

(2.38)

j=1

The square root matrices of the diagonal matrices L and A axe simply given by the square root of the elements. This system of Jacobi

coordinates

Vf"

=

belongs

f7v

and therefore

17

to

an

orthogonal

transformation:

(2.39)

20

Complements 1V

1V

EVji j

IV

E 2 Er2

and

(2.40)

=

i

i*

i=1

j=I

i=1

Let the momentum

Simfla,rly

to the

canonically conjugate to i be denoted qi. transformation of coordinates, we obtain the trans-

formation of momenta

follows:

as

N

71i

=

N

E ViiPi,

A

E Viini

=

j=I

(2.41)

j=I

The total Idnetic energy does not take to q and can be expressed as follows:

diagonal

a

form with respect

I?

E Mi

E E (VLfr) ij?7i -77j wLf7rl.

i=1

i=1

j=I

The two systems of the Jacobi coordinates ical Jacobi coordinates X

=

For

ujf '

a

=

=

M1

rT; 1'2

?T 1 M

M2M3

3

M123

12MI23

VMM1232:

1

2

particles with equal I

1

(2.43)

V

vf2-

I

I

v/6-

T6

matrix V reads

0

12

M12

M123

I

'1

73T

disadvantage

masses

mi

axe

M3

mass

2

V"6_

(2.45)

1

73

of the canonical Jacobi coordinates

is that if the

equal then the center-of-mass motion is not sepais not the center-of-mass coordinate).

not

easily ( N

(2.44)

V-Ml'23

-

v/3-

as

0

-

V/2-

rated

=

V(Uj)-Ix.

VMM1123

The

can

-VEM12

L2 M12

and for

Vr

Ujr and the canoneasily be related by x

three-paxticle system the transformation

V

(2.42)

=

3. Introduction to variational methods

The variational method is

popular approaches to tackle quantum-mechanical few-body problems. Though it gives only an approximate solution except for some special cases (the Ritz variational method, for example, gives only an upper bound of the energy), one can get a virtually exact solution with an appropriately chosen function space. The function space is defined by basis states and the wave function of the system is expanded in that, basis. In this chapter we briefly introduce the theorems requisite for obtaining a vaxiational one

of the most

solution.

3.1 Variational Let

principles

physical system whose Hamiltonian H is self-adjoint (Hermitian), bounded from below and time-independent. We are interested in finding the discrete eigenvalues of H and its corresponding (normalized) eigenstates: us

consider

H!P,, The

=

a

En(fi,

energies En

n

axe

=

(3.1)

1, 2,...

real and

are

ordered such that El :! E2<

....

We

that the ground state is non-degenerate. Although H is known, this does not mean that E,, and (fin axe known. In general, it is difficult to solve the eigenvalue equation (3. 1). When we do not know how to diagonalize H. exactly, the vaxiational assume

method becomes useful for any

Theorem 3.1 the state space the is such that E

=

RIHITI) R_ I TI)

type of Hamiltonian.

(Ritz Theorem). For an arbitrary function Tf of expectation value (Mean value) of H in the state Tf

> -

El,

Y. Suzuki and K. Varga: LNPm 54, pp. 21 - 37, 1998 © Springer-Verlag Berlin Heidelberg 1998

(3.2)

3. Introduction to variational methods

22

where the

equality

if and only if Tf

holds

is

an

eigenstate of H

with the

eigenvalue El. Proof.

elementary and can be found in of quantum mechanics. See for example [1, 2]. The ftmetion expanded in terms of the energy eigenstates

The

textbooks T1 may be

proof

of this theorem is

00

(3-3)

ai(fii.

In this

cluded and the

integration

over

(Tf jHn Itp) (TrI Tf )

the

with continuous

eigenvalues are sum must be extended appropriately to include them. Then we can show that for an integer n

expansion

eigenstates

0

Faci=2 A Eln)Jai 12 00, jai 12 Ei= n Y

inan

7

-

En I

-

-

(3-4)

I Clearly the right-hand side of Eq. (3.4) is non-negative for n and if for > if i It vanishes 2. > 0 because Ei 0 for E, only ai i > 2, that is, T, is an edgenstate of H with eigenvalue El. This proves I was used to prove the Ritz the Ritz theorem. Only the case of n theorem but other cases will be needed later to derive Temple's bound. =

=

-

=

approximate deexploited as ground-state energy El, namely the minimization principle of the mean value of H. Suppose that we choose a family of functions Tf (a) which are characterized by a finite number of parameters denoted a. In the case of Eq. (1.1), there axe two parameters a and P. We calculate the mean value E(a) of the Hamiltonian H in this trial function, and minimize E(a) with respect to a. The minimal value obtained in this way is an approximation to tile ground-state energy El of the system. Clearly, whether this variational method produces a satisfactory result or not substantially depends on the choice of the trial functions Tf (a). The Ritz theorem can be generalized to excited states as well: The Ritz theorem is the basis for

a

method of

it is

termination of the

Theorem 3.2

(Generalizecl

of the Hamiltonian H discrete eigenvalues.

value

Proof.

Let

E(TfIT)

=

us

(TfjHjTf)

sumed to be linear term

calculate

an

is

Theorem).

stationary

in the

increment JE of the

The

expectation neighborhood of its

mean

value us' g

+JT-1, where JTf is aschanged of higher order than a terms Neglecting

when Tf is

infinitely small. in JT1, we obtain

Ritz

to Tf

3.1 Variational

(TfITf)JE

=

=

The

(JTf IH

value E is

mean

that

J((TIIHITI)) -

-

23

principIcs

EJ((TIITI))

EITI)

+

(TfIH

stationary if JE

(3.5)

EIJTf).

-

=

0 for any infinitesimal

JT,

if

is,

(,NTtIH

EITI)

-

+

(TIIH

If JTf is chosen to be

the above

number,

-

-(H

EIST)

-

E)Tf,

(3.6)

0.

=

where

-

is

that the

equation implies

an

infinitesimal real

norm

of the function

(H E)Tf is zero, and thus the function (H E)Tf itself must be a null function, namely HTf = ET. Therefore the mean value E is -

-

stationary if and only if the state Tf from which E is calculated is an eigenstate of H, and the stationary value E is the corresponding

eigenvalue

of the Hamiltonian.

generalized Ritz theorem allows an approximate determination of the eigenvalues of the Hamiltonian. If the E(a) has several extrema, they are the approximate values of some of the energies E,,. In most cases for practical applications the. trial function is given as a linear combination of a finite number of independent functions This

!P(a): K

(3.7)

ciTf (ai).

Tf

independence of the functions will be discussed soon later. T' (a K) axe mutually orthogWe do not always assume that Tf (a I) onal because the use of nonorthogonal. functions is in fact quite useful. They can, however, always be made orthogonal if necessary, e.g. by a Gratn-Schmidt orthogonalization procedure. The variational method then reduces to the eigenvalue problem of the Hamiltonian inside the state space VK spanned by the set JTf((YI),...,Tf(aK)Ji that is, the space containing all linear combinations of T (a,), Tf(aK). The mean value E is given by The linear

,

...

i

...

Ctlic E

(3.8)

=

CtBC' where and

-

c

is

a

IC-dimensional column vector whose ith element is

ct is the Hermitian conjugate of c. The K

overlap

matrices W and B

are

defined

by

x

ci

K Hamiltonian and

3. Introduction to variational methods

24

Rij

=

(Tf(ai)JHJT'(cvj)),

Bij

(TI ((Yi) I Tf (aj)).

=

(3.9)

The linear parameter ci can be determined by the generalized Ritz theorem. The condition that E is stationary with respect to an ar-

bitrary, infinitesimal change problem

of ci leads to the

generalized eigenvalue

K

Wc

E&,

=

E(Rij

i.e.,

-

EBij)cj

=

0

(i

=

I,-, K).

(3.10)

j=J

The restriction of the thus

can

eigenvalue problem

of H to the

subspace VK

the solution.

simplify

We discuss the linear Tf (a K). The linear c

except for

c

0

=

can

function. In other

and

only

for

has

E

c

K

if c

independence of the functions Tf(al),..., independence of the functions means that no vector make

words,

0. This is

=

a

linear combination ,

EK i=1 ciTf(ai),

the combination becomes

equivalent

unique solution of c ci!F(ai) 0 is equivalent a

=

=

0.

a

a

null

null function if

that the

equation Bc 0 (To understand this, we show that

to

to Bc

saying =

0. Whe'n

=

EK ci!P(ai)

=

0,

0 for j obviously have Ef I ci (TI(aj) JTf (ai)) I,-, K, which but for 0 nothing j I,-, K. Conversely, when (Bc)j (&)i 0 for j I,-, K, by multiplying cj* (the complex conjugate of cj) and we

=

is

=

=

=

=

=

summing

over

j,

we

obtain ctL3c

=(.EK CiT,(Cv,) I EK I

K

which leads

us

solution

0 for the

Fj-1 ciTf (ai)

1

ciTf (ai))

=

0,

As the existence of

a unique 0.) equation Bc 0 is possible only when detB --A 0, the linear independence of the functions is assured by the condition detB :A 0. Because the overlap matrix B is at least positivectBc > 0 for any vector c, all eigenvalues semidefinite, that is (Tf JTf)

c

=

to

=

=

=

p of B become

Tf (a K) ar e real, positive when the functions Tf (a,), linearly independent. The positiveness of M is understood as follows: For the eigenvector c :A 0 corresponding to the eigenvalue JL, we have the relation pctc As the basis functions Tf are (Tf Ifl. linearly (ai) independent, Tf is not identically zero because otherwise we can make !rf EK ciTf (ai) vanish identically with c =A 0, which contradicts the i= I assumption of the linear independence of the basis functions. Thus (TfITf) is positive and of course ctc is positive, so the eigenvalue y has to be positive. We can also state that if there exists a vanisl-iing eigenvalue of B then the basis set JTf(a1),..-,Tf(aK) is linearly dependent. The solution of the eigenvalue problem, pc(A), gives us an ....

=

=

BcG l

orthonormal set:

=

3.1 Variational

principles

1: C(ii.') Tf (C'j),

01.1

25

(3-11)

2

i=l

where

c(l')

c(") tc(/")

is assumed to be normalized to

=

1. In many

practical problems it may happen that B has one or several very small eigenvalues. Then the eigenstate corresponding to the small eigenvalue has very large expansion coefficients cil") If this occurs then a - Flj,. small error in the matrix elements of R or B can lead to a larger error in the solution of Eq. (110). When the ill condition mentioned above does not occur, the generalized eigenvalue problem (3.10) can be solved safely. The eigenvalues q

(i

est

1,

=

...'

K)

eigenvalue

are

arranged be

El may

a

in

increasing order el :! good approximation to

62

:

the

The low-

...

ground-state

energy El if the state space V_T<- is chosen to include the physically most important configurations. Two functions T and TI' belonging to

the

and ej,

eigenvaluesq

(Tf I Tfl) where

CtBC'

-md c'

c

Rc

=

=

have the

overlap

(3.12)

1

satisfy

EiBc,

respectively,

the

and

following equation

'Hc

=,EjBc'.

(3.13)

I and likewise T', c has to be normalized to ctBc &t&' 1. Using the Hermiticity of R and B and the reality of the 0. Thus eigenvalues Ej in Eq. (3.13) leads one to (Ej cj)ctBc' the two eigenstates belonging to different eigenvalues Ei and ej are orthogonal. In the case of degeneracy, they can be made orthogonal by an appropriate procedure. The relationship between the eigenvaluesEi of the truncated problem and the eigenvalues E,, of the full Hamiltonian is elucidated by

To normalize

=

=

=

-

the Nfini-Max theorem. Theorem 3.3

(Mini-Max Theorem).

operator with discrete eigenvalues El :5 E2

eigenvalues of H restricted to independent set of K functions Tf (a,),

EK be the

the

...

E2:51E2i

El <'Eli

...

i

EK :

I

<

Let H be ....

a

Hermitian

Let El ! e2 <_

subspace Vrc of

Tf(aK).

a

-

<

linearly

Then

16K-

(3.14)

Proof. Let WK be the subspace spanned by the orthonormal eigenstates!Pl,(k I!PK of the operator H. We will first show that there ...

is at least

one

normalized function in Vrf with the property

3. Introduction to vaxiational methods

26

(TfJHJTf) To show this

p

WK;

(3.15)

consider the projected function PTf for any normalized VK, where P is the projection operator that projects

we

function Tf in onto

EK.

>

=,EK I!Pi) (!Pi 1. i= I

There

are

two

(i) there exists a function Tfo in Vr<- such (ii) PTf :A 0 for all functions T, in Vl<-. In

case

(i) Tro

is

a

(ii)

that

PTfo

=

0.

linear combination Of 43K+1,

the normalized Tfo has the case

possibilities:

T)lf+2,..., and hence (Trollll%) : : EK+, ! EK. In fimetions Tf, and Tf2 in Vl<- are

value

mean

any two different normalized

projected to different functions PTfl and PTf2 in _PVK because otherwise P(TV, Tf2) 0, which contradicts the assumption. Namely, any two different normalized functions in V.[<- axe projected by P to different functions in Wl,(. As both VK and )IVI<- have the same dhnension, it follows that there must exist a normalized function T, in V.Tf with the wPrf (a 4_ 0). Then !Tf can be expressed as a!PK + bo, property M =

-

=

where

0 is a PK+1,!PK+2,

(TfJHJTf)

=

normalized flinction

Next

2!

we

;

a

linear combination of

=

(T'IHIT')

largest eigenvalue >

of H restricted to

EK)

V_Tf,

Ell;C.

we

EK.

Vif which

by induction

It is easy to derive the

have

(3.16)

(K- I)-dimensional state space Vr.C-1

of all those functions in to 45K and

value,,.-

mean

_

define the

belonging

as

1. This function has the JaJ2 + JbJ2 Ja 12EK + lb 12(01H10) Erc + lb 12((01H10) ...

Because 16K is the IEK

given

are

can

following

orthogonal

show 'EK-1

to be the set

to the

eigenvector

! EK-1 and

so on.

theorem ft-om. the Nfini-Max the-

orem.

Theorem 3.4. Let E,

of

the lowest

! , E2

<

EK be

a

number K

Hermitian operator H. Let

eigenvalues of be a set Of linearly independent functions. a

Tl(a2)i..., Tf (aK)

Tf(al),

Then

K

1: Ei :! Tr(B`R),

(3-17)

i=1

where the matrices B and R

Proof. to

the

Let el :

162

subspace Vl<-

:5

---

:: -

are

defined by Eq. (3.9).

IEK be the

of H restricted

eigenvalues

of the K functions

Tf(Cfl),

...

i

Tf (Ci K) and let

3.1 Vi-triational

be the orthonormal.

eigenvalueS

6 11

E21

...

16K. Then

i

Oi

is

principles

27

eigenstates corresponding given by

to the

K

E UijT1(aj)

(3.18)

j=1

with U orein

the

satisfying

3.3

orthonormality condition UtBU

K,

K

J:Ej

=

1. From The-

obtain

we

K

EEi=E(OilHloi)=Tr(UtHU)=Tr((BU)-IHU)

:5

Tr(U-'L3-1WU)

=

Tr(B-1R).

(3-19)

right-hand side of Eq. (3-17) is determined only by the subspace spanned by the functions and not by the particular choice of the basis because any non-singular linear transformation of the basis does not change the trace (3.17). Namely, when a new basis It is noted that the

set Xl,...,XK is

K)

with

a

FC

given by a transformation Xi Ei= J Tij Tf ((--ij) (i T matrix non-singular (deff :A 0), we can show that =

Tr(B-'?i),

where

L3i'j

-

21

(XilXi)

and

R'ijtj

=

(XjjHjXj).

formalism where the

This leads to the

density can density-functional calculating the energies of excited states as well as the ground state. See [4, 5] for this interesting idea. The next theorem is fundamental to answer a question of how the eigenvalues obtained in a restricted subspace change as the basis be used

as a

basic vaxiable for

dimension is increased. Theorem 3.5. Let el ! - 162 mitian operator H restricted to the

of independent functions EI

K+1

be the

subspace VK of linear combinations

Tf (a,), If (a2),

...

i

Tf(01K).

of H restricted to the

eigenvalues of independent functions

combinations

Let El <

e2

:5

subspace VTC+l of

Tf (01)i llf (a2),

...

7

...

<

linear

Tf (aK), and

Then

!P(OK+I).

Ell

:! 'EK be Hie eigenvalues of a Her-

< El

:5

E12

:-5

C:2

:5

...

:5 '61K :-5

61K,(+i*

(3.20)

OK be the orthonormal eigenstates correspondProof. Let 011 02 16K- Any function !P in VK+j can be ing to -the eigenvalues 61,162 expressed as 1

...

i

K+1

Tf

CA,

(3.21)

28

1 Introdnetion to variational methods

where the normalized function inake, it.

orthogonal

01-<-+,

is constructed from

to any function in

Tf(aK+l)

Vfc: K

(Tf (a

OIC+I

to

2

1 (0i I Tf (Ct 1,;C+l 12

Tf (a 1,C+ 1))

K

(3.22)

x

The the

eigenvalue problem using simple form 61

0

0

62

-

0

-

0

the basis set

)

h, h2

takes

)

C,

)

C1

C2

C2

=E 0

0

-

h *1

h;2

...

EK

hK

CK

h I*c K

hrc+1

CTC+I

CK

CJf+

(3.23) where

hj

=

%JHJOrc+I) and hj* is the complex conjugate of 11j. The D(E) to determine the eigenvalues reads as

characteristic function

K

D(E)

(hK+1

-

K

E) II(Ei

-

E)

K

II(Ei

-

E)

hIc+i

i=1

(i

Ih-I2 EJ

_

E)

0.

E

(3.24)

I,-, K) axe nonzero. The (K + 1) obtained by finding the roots of the equation K

E-hK+I

E

-

j=I

Here it is assumed that all hi are

-

11 (Ej

Ihi 12

-

K

eigenvalues

K

=

Ihi 12 E

-

(3.25)

ei

The right-hand side of the above

equation becomes negative for E

< C,

and in

positive for E > CK. A graphic solution of Eq. (3.25) is displayed Fig. 3. 1. It is clear that the cross points of curves, namely the new

eigenvalues E , satisfy the relation (3.20). When there are n vanishing hi's, the corresponding ei's become the solutions of Eq. (3.23), i.e., E'i Ei. The remaining (K + I n) new ==

-

3.1 Variational

1N

29

principles

2

'=1E-Cj .................

.......I.. ............V..

.........

....

F-21

611'

.....

...

...........

..................

I 'EK

E-hK+1

Fig.

3.1.

Graphic

solution of

Eq. (3.25)

to obtain the

eigenvalues

of

Eq.

(3.23)

eigenvalues the

same

are

structure

also in this

through the eigenvalue. equation, which has Eq. (3.23). The relation (3.20) trivially holds

obtained as

case.

The significance of this theorem is

that, by including a further term in the basis, the K lowest eigenvalues; cannot become worse. Therefore, this theorem implies the Mini-Max theorem because, in the limiting case that the subspace approaches the full Hilbert space as the basis dimension increases, the K lowest-eigenvaluesEj converge to the exact eigenvalues; of the Hamiltonian. Suppose that one wants to see how the lowest eigenvalue changes when one vaxies only the (K+l)th function-!V(arc+j) while keeping the rest of all. the K functions unchanged. In this case one does not need to solve the generalized eigenvalue problem of type (3. 10) but only needs to find the smallest root of Eq. (3.25). -Of course the latter is much simpler and faster than diagonalizing the matrix. This advantage is used to sample more random trials in selecting a suitable basis function in the stochastic variational method, as explained in Sects. 4.2.5 and 4.2.6.

30

3. Introduction to variational methods

3.2 The variance of local energy It would be nice if there

method to

judge the accuracy of variationally. The expectation value E is the upper bound of the ground-state energy El. If we can calculate a lower boun,d, the. difference between tile, two bounds gives an estimate for how dose E may be to El. This makes sense if and only if the lower bound can be calculated as closely as possible to the ground-state energy. In order to discuss the lower bound, we define the vaxiance of the energy expectation value, o-', by the norm of the residue function were a

the solution obtained

(H

E)TfI(Tf JTf) '21

-

2

(T1J(H-E)2JTf) (TIITf)

-

0'

According

to Weinstein

(TfJH2JTf) R- I Tf

[6, 71

the

following

Theorem 3.6. There ii at least val

[E

theorem

exact

one

(3.26) can

eigenvalue

be

proved.

in the inter-

o-J.

o-, E +

-

E2

-

Proof. By using Eq. (3.3),

the variance

can

be

expressed

as

EMI (Ei E)2 JaiJ2 Fli= 00, JaiJ2 -

2 0'

_

Suppose that Ek

is the

(3.27)

eigenvalue which is

00

i

we

we

have

CO

J:(E Thus

closest to E. Then

2

_E

jai 12

have o-2 >

>

(Ek

(Ek -

-

E)2

E)',

jai 12.

(3.28)

which proves the theorem.

The Weinstein criterion guarantees that there is

an

eigenstate

whose energy is in the interval [E G-, E + o-] but does not indicate which one. In case E is sufficiently dose to the ground-state energy, -

the theorem E-

G-

<

gives

the lower bound

as

El.

(3.29)

Another lower bound called

Temple's

in terms of the variance of the energy

bound

[8]

is also

expressed

as

0'

E

<

-

e-E

-

El.

(3.30)

31

3.2 The variance of local energy

is the energy such that E < e < E2, where E2 conserved quantum energy of the first excited state which has the same numbers as the ground state. The best bound is clearly obtained by Here

-

setting

is

an

e

equal

arbitrary

to

E2. Temple's bound is easily derived

as

follows:

0.2

(E- --E )

E,

1 =

-

e

-

I

E

[

-

(,- + Ej)(E

-

Ej)

+

(TI I H2 I TI) (Tf I Tf)

EZ i=2 (Ej-,-)(Ej-Ej)jajj2 E Ei= 1 jai12

>

00

where

use

Eq. (3.4)

is made of

for E

(TfIH2lTf)l (Tflyf-) _EJ2 (with n 2). The two bounds, (3.29) and (3.30),

-

(3.31)

0,

(with

El

2]

Elf

n

=

1)

and for

=

indicate that the trial function

2

gives the smallest value of (7 is best among various trial functions giving the same expectation value. Temple's bound often gives better that

lower bounds than the Weinstein bound. See

[91

for the extension of

variational bounds. The variance of the

expectation

value

can

also be defined

through

the local energy HTf

Ej., (R) ,

!P7

(3-32)

I

where R stands for the

"configuration?'

of the

particles.

More precisely,

by ri and pi, where pi particle stands for the coordinates other than the position coordinate ri, then R stands for Ir I i P1 ilr2) P2 i 1. The variance defined by Eq. (3.26) is equal to the variance of the local energy if the coordinates of the ith

are

denoted

...

(TfjjEjo,(R)

2 0'

-

E121!Tf)

=

P(R)IEI.,:(R)

-

Ej2dR (3-33)

with

P(R) where as an

E

--

I Tf (R) 12 R I Tf)

(3-34)

energy of H in the state local energy: of the average

E, the

=

mean

(TIjEjo,(R)jT1) 010f)

-

Tf,

I P(R)Ejoc (R)dk

can

also be rewritten

(3.35)

3. Introduction to variational methods

32

Here

P(R),

uration

the

probability density of finding the system at the configpoint R, is non-negative and satisfies the. relation f P(R)dR

1.

H the trial function Tf is the exact

ground state of the Hamiltonian,

the local energy becomes R-independent and equals the ground-state energy El. A similax statement holds for excited states as well. If Tf is

the exact to

eigenstate

E,,. This

with

opens up

energy-&, the. local energy would be equal another possibility of the vaxiational method

instead of the minimization of the

mean

energy: The niinimization of

the variance of the local energy [101. The adjustable parameters of the trial function may be varied to minimize the variance. The calculation of the variance is in general much more difficult than that of the mean energy. An advantage of minimizing the variance of the local energy is, however, that the quantity to be minimized has a known lower bound,

Since in any eigenstate the vaxiance of the local energy is zero, this minimization principle applies to obtain excited states as well as the ground state.

namely

zero.

The

condition for o-' is obtained

stationarity

increment So-' in the

Theorem 3.2.

same.

way

By multiplying

calculating the increment following equation

to

(Tf Jqf-)jO.2 =,6((Tf JH2 Ifl) =

(,5qf- I H2

_

=

(JTf JH2

-

(Tf JH2

+

Here

-

E2

_

2EH + E2

mean

energy in

-

2 _

Eq. (3.26) by (Tflfl and change in JTf, we obtain the

linear

a

_

done for the

as was

an

both sides of

J(E2 (Tf IT,))

0.2 1 Tf) +

2EH + E

by calculating

(Tf I H2

-

_

E2

0.2j((T1JTf))

_

0.2 1 jqf-)

-

2E(Tf JTf) JE

0.2 1 TI)

0.21,5fl.

(3.36)

is made of

Eq. (3.5) in the last step. The stationarity condiequivalent requiring (H2 2EH + E2)(y 0.2TI. When the trial function is given as a sum of a finite number of functions Tf (a) as in Eq. (3.7), this condition reads as the following equation which use

tion is

can

to

=

-

be used to determine the linear parameters ci

(Q

-

2EW +

E2L3)C

=

0.2BC7

Qij

=

(!rf(a,) 1112 1 Tf (Cj)).

(3.37)

Since E defined

by Eq. (3.8) depends on c, the matrix in the round equation also depends on c. Therefore the parameter c must be determined self-consistently: One assumes an initial value for c, calculates the energy-R, and solves Eq. (3.37) to deterbracket of the above

mine

c

and 0-2. As the value

c

obtained in this way may in

general

3.3 The virkd theorem

not be

equal

to the initial

c

value,

one now uses

the solution

33

c as

the

initial value and repeats this cycle until both values of c become the same. The minimization of o-' becomes cumbersome even though the calculation of

Qij

is feasible.

The variational Monte Carlo

(3.35)

to determine the

mean

method of the

(VMC)

calculations

employ Eq.

energy. Tlie VMC method [111, or the of Two-body correlations into Multiple

Amalgamation Scattering (ATMS) [121 similar to it, usually chooses a trial function that attempts to incorporate both the sfi7ort distance behavior and the asymptotic behavior of the correct wave function, leading to complicated functional forms. Thus the analytic evaluation of the matrix elements is in general hopeless. Instead, the VMC requires only the evaluation of the wave function and its Laplacian to determine the local energy. If the interaction between the particles contains the spinorbit force, the first derivatives of tl-ie wave function are required as well. These derivatives are obtained numerically by appropriate difference formulas. The mean energy is then estimated by a Monte Carlo

integration. The sampling of a set of configuration points R is made by, e.g. the Metropolis algoritl-nn [131. The accuracy of the VMC or ATMS calculation is limited by the choice of the trial function as well as by the statistical error inherent in the Monte Carlo integration. To reduce the statistical error one has to sample a great number of points, which is computer time consuming. To optimize the variational parameters of the trial

wave

repeat the mean enof parameters. This is a hard job

function

one

ergy calculation using a different set considering that the VMC or ATMS has

particularly

in the

case one

has

The variational method is

which

can

be

adapted

has to

an

inherent statistical

error

number of parameters. very flexible approximation method

a

a

to diverse -problems. The variational method

physical intuitions lead us to an idea of particularly the qualitative form of the solution. It easily gives good values for the energy. The variational solution may, however, present unpredictable erroneous values for other physical observables. It is unfortunately valuable when

is

very difficult to evaluate their

error.

3.3 The virial theoren, summarize two theorems, the Hellmann-Feyntnan theorem and the virial theorem, which are valid for the exact solution.

In this section

They

can

we

be used to check the

quality

of the

wave

function.

3. Introduction to variational methods

34

Theorem 3.7

(Hellmann-Feynman Theorem).

Let

H(A)

be

a

Hermitian operator which depends on a real parameter A, and POO a normalized eigenstate of H(A) of eigenvalue E(A). Then the theorem states that

d

TA E(A)

=

(3-38)

( P(A)J DA

Proof. Differentiating,

with respect to

A,

the relation

(3.39)

E(A) we

have

a

d

dA

E(A)

=

( P(A)J

(9A

H(APKA)) 19

(9 +

OX The Iast two terms

(fi(A) IHN ON) on

the

+

R(A) W(A) 1

(3.40)

A

right-hand side. of Eq. (3.40)

vanish because

a

(9

PNIH(A)O(A)) E(A)

+

OPNIHNI

J-P(A))

IN

+

CA))

(!P(A) I OA jA-

P(A))]

d =

where

use

E(A) d,X ONON)

=

(3.41)

01

is made of the conditions that

H(A)!P(A)

When the evaluation of the matrix element of the

theorem

E(A)!P(A)

H(A)

and

does not

be used to

Oficulty, Hellmann-Feynman consistency of the vaxiational solution. If H(X) Ho +,XHI, then the matrix elements needed are just the terms of the energy expectation value. It is straightforward to generalize the 11611mannFeynman theorem to the case that the Hamiltonian contains a number of parameters AI A2 We note that the 11ellmann-Feymnan theorem can be stated in an integral form pose any check the

=

7

E(A2)

can

-

E(Al)

=

(!P(A2)JJff(A2) (!P(A2)J!P(A1))

3.3 The viri.-,U theorem

(3-42)

OA

"1

35

equality is trivial for the exact solution and has nothing to do with the I-Iellmann-Feym-nan theorem. The equality holds, however, only approximately for the variational solution and may be used to check the quality of the solution. The following theorem plays a key role in the derivation of the The first

virial theorem. Theorem 3.8. Let (P be

For any operator A

(T)I [H, A] I!P)

=

we

eigenstate of a Hermitian operator

an

obtain

(3.43)

0.

proof is easily obtained by noting

The

H!P

E. To test the accuracy of the vaxiational special operator of the form N

N

.

A=

=

ET, with

solution,

one

eigenvalue

often

uses a

(9 ri

ri-pi

h

H.

(3.44)

-

r. 'ri

i=1

because the commutator

[H, A]

is

easily calculated. We

operator A is a generator of the dilation operator, property, in a single-variable case,

e

aA,

d

exp

(ax dx ) f (x)

=

note that the

which has the

(3.45)

f (eax).

by expanding f (x) in power series and using for any integer value of n. valid nkXn, dX Assume that the Hamiltonian for an N-particle system takes the

This is

easily

(X_A_)kxn

shown

=

form N

H

Whether

or

Pi

E=I2mi

T+ W

=

-

T,,

.

+

W(ri, r2,

can

potential

W is assumed to contain

no

C7 ri-

Ori

P2(-2mi

-Pi'IrN),

'n Ar M12 --N ..

on

(3.46)

the virial theorem.

momentum

then show that

IT,

rN),

not the center-of-mass kinetic energy is subtracted from

the Hamiltonian is irrelevant to the discussion

The

.--,

operators. We

3. Introduction to variational methods

36

1W,

0

ri.

where M12

...

OW

1 c9ri N=

'=

(3.47)

-ri-

ari

EN

mi

is the total

EN

is the total momentum. ..,i= I Pi we obtain

of the system and 7rN

mass

Using Eqs. (3-44), (3.46)

(3.47)

and

N

aw

[H, Al

=

2T

-

with

WA

WA

(3.48) ri

i=1

Substituting

this into

Theorem 3.9 the Hamiltonian

2(!PjTjfl Therefore

77

a

-

(The

(3.46).

virial

Theorem).

following

Let!P be

theorem.

an

eigenstate of

of Eq. (3-44)we

obtain

0.

=

z7 defined

quantity

leads to the

For the operator A

((fijWAj(fi)

(!PIWAI'P) 2(!PjTj!P)

=

Eq. (3.43)

(3.49) by

'

1

(3-50)

vanishes for the exact solution and

be used to check the

can

quality

of the solution.

One has to know WA to make use of the virial theorem. It becomes particularly simple if the potential is a homogeneous function of degree s,

namely

W(Ar I Ar2

ArN)

i

=

i

=

because then

ating, to X

=

A*W(rjr2,

...

I

7 ....

ATNi AM AZN)

rN)7

(3.51)

obtain

with respect to

by the use of Euler's theorem or by differentiX, both sides of Eq. (3-51) and setting A equal

I

WA In this

we

W(AX1 AY1 AZI

=

SW-

special

(3.52) case

Eq. (3.49), together

yields the well-known

with

(!PjTj!P) + ((fijWjfl

=

Ej

relation 2

((!PITI! P) s

Because the

tial

(s

=

+2

E,

PIWI(P)

E

=

s+2

(s :A -2).

(3.53)

homogeneity condition is fulfilled for -the Coulomb potenthe quantity t7 is conveniently used to check the quality

-1),

3.3 The virial theorem

of the solution for

37

system of particles interacting via Coulomb

a

po-

tentials. For

a

general non-homogeneous potential IV

N

W(rwr2,

Ui(ri)

'rIV)

...

must be

E

+

i=t

Eq. (3.52)

Vij(ri

(3.54)

rj),

replaced by

Oui(r)

WA

-

i>i=l

N

IV

function of the form

r-

Or

)

OV,ij (r)

(r

+ r=ri

Or

)r=ri-rj (3-55)

spherically symmetric potential the operator r-ar- reduces simply r-4-. If the calculation of matrix elements of the. operator WA is not dr

For to

a

difficult,

the virial theorem

When the

potential

W

can

be used

depends

as

on a

parameter A,

(9

(!PIWAI(P) Here the

=

((filWA

+A

in the Coulombic we

case.

obtain

d

WI-P)

-

A

dA

(3.56)

E(A).

theorem is used to express the expecW in terms of the energy eigenvalue E(A). In a

Hellmann-Feynman

tation value of

A'&

molecular system X may be a set of parameters which stand for the positions of nuclei and if W consists of only the Coulomb potentials

-W simply reduces WA + A-bX plication

of this relation.

to -W. See

Complement

8.2 for

an

ap-

4. Stochastic variational method

approach to the variational solution of quantumproblems is to diagonalize the Hamiltonian in a state space spanned by some appropriate functions TV (a-,) Tf (a2) Tf (CeK). The applicability of this approach is, however, very limited, because the diagonalization may not be feasible if the dimension K of the state space is very large. This is typical in many-particle problems

The most direct

mechanical bound-state

7 ...I

I

such

as

the Hubbard model

or

the nuclear shell model. This method

approach", because one sets up a basis in a well-defined way, e.g., by using a complete set of states that contains no parameters, and then obtains the energy by a diagonalization. Another possibility is basis optimization, which is actually designed to avoid the problem of the huge basis dimension in the direct approach. In this case one specifically selects the basis states that are really essential to get the energy and the wave function of the syscan

be called

a

"direct

certain accuracy. It is obvious that this selection may be state-dependent: Some functions might be adequate to describe the

tem to

a

others would be

appropriate to approximate an excited state, particularly when the ground state and the excited state have different spatial extensions. The stochastic variational method uses this second route by selecting the most appropriate basis functions in a trial and error procedure. but

ground state,

4.1 Basis

some

more

optimization

It goes without saying that the quality of the variational approximation crucially depends on the choice of the basis functions. Our

primary aim here is-

choose basis functions 1.

They

can

be

IV-particle problems. For this that meet the following requirements:

to solve

easily generalized

for

Y. Suzuki and K. Varga: LNPm 54, pp. 39 - 63, 1998 © Springer-Verlag Berlin Heidelberg 1998

an

N-body system.

we

will

4. Stochastic variational method

40

2. Their matrix elements

3.

They

are

analytically calculable. easily adaptable to the permutational symmetry are

of the

system. 4.

They

are

flexible

enough

to

approximate

even

rapidly changing

functions.

important condition (3) is non-trivial because the permutational symmetry looks very complicated when expressed in terms of the relThe

ative coordinates to be used.

A

possible

choice for the basis functions

tions is the correlated Gaussian of

fillfilling the

above condi-

Eqs. (2.23)-(2.25):

-1 N-1

1

c

exp

Ax)

NE E Aij

exp

i=1

xi

-

xj

j=1

IV

expf -2

E

aij (ri

-

(4.1)

rj

i>i=l

equivalently, aij are nonlinear paxameters are spherically symmetric. To take into account non-spherical states, the basis function has to be multiplied by an appropriate orbital angulax function. In addition to the spatial degree of freedom, the particles may have other degrees of freedom, such as spin and flavor, and thus the function has also to be multiplied by suitable trial functions in these additional spaces. These functions may bring other parameters or sets of quantum numbers. These sets of quantum numbers (e.g., total and intermediate spins, orbital angular The matrix elements

Aij

or,

of the basis. These functions

momenta,

etc.)

be considered

can

often be referred to

as

trial function will be

as

channels in the

given

in

discrete parameters, and will following. (More details on the

Chap. 6.)

The actual form of the basis function is not very important at this stage. The above discussion serves to draw the reader's attention to the fact that the basis function

depends

on

many

and discrete parameters. The parameters define the

linear, nonlinear shape of the basis

function and determine how well the variational function space contains the true eigenfunction. To find the best possible solution, one has to

optimize the paxameters. To have a crude guess of how much optimization amounts to, let us consider an N-particle syswith the simplest basis function (4.1). This correlated Gaussian

work the tem

has ea,r

N(N

-

1)/2 parameters, and, by assuming

combination of K

functions,

-we

face

an

that

we

need

a

lin-

optimization problem of

4.1 Basis

K(N(N 1) /2) -

the number of

41

paxameters. Tb is number increases quadratically with

particles. By taking

N

=

4 and K

end up with 1200 parameters. The main problem of the minimization of

case,

optimization

=

200

as a

typical

we

nipresence of local minima. A local function reaches

a

minimum in

a

There

function is the

om-

point where the

finite interval of variables and the

number of such minima tends to increase

of the

a

minimum is the

exponentially

with the size

are plenty problem. optia function, and these optimizations can be divided into two categories: the deterministic and the stochastic optimizations. A deterministic optimization moves downwards on the slope of the function according to a certain well-defined strategy. There exist many elaborated algorithms (conjugate gradient, Powell (direction set), etc. [141) and they are deterministic in the sense that, starting from a given point, they always reach the same (local or global) minimum. The drawback of these techniques is that they are time consuming and tend to converge to whichever local minimum they first encounter. The solution in these cases may not be the global minimum but a local minimum. These methods are sensitive to the starting point and are

of different methods for the

mization of

unable to search further for

a

better solution after

a

local minimum is

reached.

Stochastic optimizations address the problem of finding the global large number of undesired local minima

minimum in the presence of a by making random steps [15,

161.

One can, for

example, start deterstarting points and then pick up the minimum of these. Numerous strategies have been developed in the last few years, e.g., simulated annealing [171, genetic algorithm [18] etc. The simplest (and actually not very economical) stochastic optimization is a random search where one picks up random points and tries to find the minimum. This may not sound very sophisticated, but the optimization with a random trial and error procedure seems to be the most efficient one. In some cases it would be nearly impossible to apply other strategies than simple random trials. To reduce the load of optimization, an alternative is to shift the burden of minimization from a large number of parameters to a smaller number of more sensitive, "tempering", parameters. Several such possibilities have been explored, e.g., geometric progression [19, 20], random tempering [21, 22, 231, and Chebyshev grid [241. The common property of these methods is that they use a "grW in the parameter space. The grid is given by some ad hoe rule and each point of ministic searches from several random

4. Stochastic variational method

42

grids defines a basis function. The grid can be defined by some simple functions which may depend on some additional- parameters to be optimized. The number of parameters contained in the functions which define the grid is chosen to be much smaller than that of the original function to be optimized. For example, in the case of a three-particle system, each of the basis functions has three parameters: All, A12 A21 and A22 or a12, a13 and C923- Some COnVenient the

=

choices for basis parameters

are

shown in Table 4.1.

Table 4. 1. Choice of parameters. In the random tempering p is an index to a prime number that is used to generate pseudo-random numbers.

denote

See

Eq. (4.8) for the

Geometric

All

=

notation <

i, i

>.

progression -2

(aiqk-i) (a2q2-1) I

A22

=

A12

=

(k

mi)

(k

M2)

(k

I,- mi.)

(k

1:

(k

1

(k

17

mi)

(k

17

M2)

-2

k

0

Random tempering a12

=

OL13

=

a23

=

exp(d, < k,p > +d2 < kp + I > exp(d3 < k,p + 2 > +d4 < k,p + 3 > exp(d5 < k,p +4 > +d6 < k,p + 5 >

,

...

...

M2)

M3)

Chebyshev gTid All

=

A22

=

A12

=

( a2tan ( altan

0

7r

2k-1

2

2 mi

7r

2k-I

2

2M2

4.2 A

distribute

certain number of basis functions to

a

part of the

wave

function and then

the basis elements in

4.2 A

regions

one

43

practical example

might

approximate the bulk

increase the

density of

where finer resolution is needed.

practical example

point of the previous section, let us consider an example for basis optimization. The example will at the same time provide insight into some other aspects of the methods as well. We consider the system of a positron and two electrons, Ps-, used in Chap. 1. The energy of this system has been very accurately calculated by various To illustrate the

approaches and

it has been found to be -0.262005 in atomic units

given in a.u. throughout this chapter unless otherwise mentioned.) The quality of the different optimization strategies used in this section can be judged by comparing their results with this value. Let the positron be labelled I and the electrons labelled 2 and 3. With the electron spins coupled to S 0, the orbital of the trial function that the antisymmetry requires part ought to be symmetric with respect to the interchange of the electron coordinates. The wave function is thus expanded as

(a.u.). (Energy

and

length

are

=

K

1

Tf

=ECk(1+P23) exp (-2-;

,Akx),

(4.2)

k=1

exchange operator P23 is introduced to assure the symr2 and X2 rl metry requirement. The coordinates are x, matrix 2 with three 2 and x Ak is a symmetric (rI + r2)/2 r3, nonlinear parameters All, A12 and A22. The wave function Tf has 3K parameters to be optimized. The linear parameter Ck is determined by solving the generalized eigenvalue problem (3.10). To reach the accuracy required in atomic physics, the minimum basis size of a three-body problem is at least K 100, as will be shown later. That means that even in this simple example we would have 300 parameters. This is already almost beyond the capability of most of the computer codes for optimization and this "full" optimization is out of the question for larger systems. The fact that the optimization of a large number of parameters is not feasible is just a small part of the problem. To have an efficient optimization one needs fast function evaluation as many times as required. There are two steps which are where the

=

-

=

-

-

4. Stochastic variational method

44

necessary to calculate the energy expectation value: The calculation of overlap and Hamiltonian matrix elements and the diagonalization.

the In

a

fall

required

optimization,

one

time increases

(a K3-process)

as

has to recalculate all matrix elements K2) and to

at each calculation of the energy. This is

load

for

(the

the Hamiltonian

rediagonalize

a

considerably

small system. heavy computational Instead, one can try a partial optimization. One can, for example, fix the parameters of all basis states but one. In this partial optimizaeven

a

only one row (column) of the Hamiltonian and the overlap -nn atrix (the required time is of order K). Let -us assume that the Hamiltonian has been diagonalized over the fixed basis states. Then, in the successive step, only one row (column) is changed. As has been shown in Theorem 3.5, after the N x N diagonalization there is no need for an extra diagonalization to solve the eigenvalue problem on the (N + I)-dimensional basis. Consequently, the computational time required by the partial optimization is only a small ftaction of that of the full optimization, and, moreover, only a small number of paxameters (three in the present example) has to be optimized. tion

has to be recalculated

4.2.1 Geometric

First let can

us

try

to

progression

use a

grid defined by

a

define three different sets of Jacobi

which two

particles

are

connected first:

Sects. 2.4 and 7.6 and in these systems to be

given

Fig. by x('), X(2)

and

us

X(3)

(23)1, (31)2,

and

(12)3.

See

denote the Jacobi coordinates The trial function is

IT

assumed

in the form K

3

(P)

qf

Ckl P=1 k=1

with the

2.2. Let

geometric progression. One coordinates, depending on

exp(--l (-P)A(P)x(P))0(11)00(x(P)), 2

(4.3)

1

angular function

0(11)00 (X)

=

[Y1 (XI) X Y1 (X2)100 I

-

(-1)1-M

(4.4)

-: 2= ,+1Y1Ta(X1)Y1-m(X2)-

Here p denotes the arrangement channel and Y1. (,r) is

a

solid spherical

harmonic

YIM M

=

7"YM (P),

(4.5)

4.2 A

where Yl,,, (i

)

polynomial

a

is

a

spherical harmonic.

practical example

The solid

45

spherical harmonic is (see Complement

of degree 1 in the Cartesian coordinate

A() is always chosen to be diagonal. Therefore, the k spherical part of Eq. (4.3) is considered a special case of Eq. (4.1). (See also Complement 8.4.) The trial function of type (4.3) is used in the so-called Coupled Rearrangement Channel Variational Method [20, 25, 26]. The basic idea of this approach is that, by taking into account 6.2).

The matrix

the different Jacobi sets, one can introduce various correlations. This method has been used with great success especially for Coulombic

three-body problems [201. Because of the symmetry of the trial

function,

(2) C

(3) =

k1

The 2

x

cki

we

A (2)

may A

-

requirement imposed

on

the orbital part

that

assume

(3)

(4-6)

"k

k

diagonal matrix A(P) 1, (k K) has two nonlinear k and they are taken as a geometric progression

2

=

...'

rameters

(Ak(')),,

(P)

ai(p) (qi ) In

principle

one can use

k-1

(i

=

1, 2).

pa-

(4.7)

different geometric progression parameters,

ai(P) and qi(p), corresponding to the different arrangement channels and the Jacobi

that

is, they would depend on p and i in order even depend on the angular momentum 1. For simplicity, in this example we use the same parameters, a and q, for all. arrangement channels and all sets of Jacobi coordinates. The main reason for using the geometric progression as parametrization is clear: The number of parameters of the basis is reduced to just 2 (a and q), so the optimization is simple. Another reason for the choice of this specific parametrization is that the overlap integral of the basis functions can be easily controlled by a choice of q and thus the danger of the linear dependence of the basis functions can be avoided. (See Sect. 3 for the danger arising from the linear to

coordinates,

get better convergence. They might

dependence of the basis functions.) The disadvantage of the use of these diagonal matrices is that, without having some polynomials like the scalar product of Eq. (4.4), the energy does not converge to its accurate value. As is shown in Table 4.2, one reproduces only the first two figures (E -0.2618530) =

of the

ground-state energy without the polynomial part, i.e., by taking 0 in the expansion. only I

=

4. Stochastic variational method

46

Table 4.2. The energy of Ps- in different energy is -0.262005. E

arrangement channels. "Exact"

(a.u.)

Channel

Partial

(23)1 (23)1

1

1 =0,2

-0-2392726

(31)2+(12)3 (31)2+(12)3 (31)2+(12)3

1

=

0

-0.2609626

1

=

-0-2619622

1

=

0,1 0, 1,2

(23)1+(31)2+(12)3 (23)1+(31)2+(12)3 (23)1+(31)2+(12)3

At this moment

=

1

=

1

=

1

=

a

wave

-0.2068096

0

-0-2619717

0

-0-2618530

0, 1 0, 1, 2

-0.2619804 -0.2619816

comment is in order. As the

spherical harmonies

angular functions, complete may think that the partial-wave expansion using only one of the Jacobi coordinate sets form

set for

a

one

would be sufficient to represent the wave function. The convergence as a function of I is, however, very slow if only one set of the Jacobi slow convergence in the partial-wave expansion will also be studied in detail in Complement 11.2.) E.g., the energy calculated with the (23)1 channel using the partial waves of

(The

coordinates is used.

up to I

2 is

=

just -0.2392726, which

of the three-channel calculation

(E

higher than the energy -0.2618530) using only I 0.

is much

=

=

Since the lowest threshold of Ps- is the Ps+e- channel at the

en-

ergy of -0.25, this result indicates that this single-channel calculation cannot bind the system. Moreover, the expansion with I has for prac-

tical purposes to be truncated to low values because the calculation of the matrix elements of high I waves generally becomes more time

consuming. Table 4.2 shows that, by combining the expansion Jacobi coordinate sets, the energy converges faster and few terms of the partial-wave expansion are needed. By

in the

the first

only using

10

grid

points for A(') k be

a

600

=

(=

we have found the optimal values of the parameters to 2.6. The variational energy obtained with this 0.06 and q =

2

x

10

x

10

x

with

computational load 180300

alized

(=

x

601/2)

one

repeated

a

calculation is -0.2619816. The

particular basis

set is the calculation of

matrix elements and the solution of

eigenvalue problem

has to be can

600

3)-dimensional

a

gener-

of dimension 600. For the optimization this

few dozen times.

By increasing the basis

get closer and closer to the exact energy.

size

one

4.2 A

4.2.2 Random

practical example

47

tempering

Another

popular tempering method is random tempering [21, 22, 231approach involves the generation of (pseudo-) random numbers with the basis parameters defined by the following prescription: This

I

ak

1: dj < k, j >

exp

(k

=

1,

...,

K),

(4.8)

j=1

where <

k, j

> is a

pseudo-random numer, the fractional part of (k(k + 1)/2)V/P---(j) P(j) being a prime number in the sequence 2, 3, 5, 7,..., that is, P(I) 2, P(2) 3,... By using this tempering number I of one a formula, optimizes parameters, dj, instead of the original 3K parameters. A possible application of the formula for a three-particle case is given in Table 4.1. The origiTi of this formula is the following. One may assume that the ground-state wave function is an integral transform of some known with

=

function with

some

weight

=

function. The known function in

our case

is the correlated Gaussian and its nonlinear parameters are the integration variables. The simplest way to carry out the integral trans-

formation is to

the Monte Carlo method. The

quadrature points integration can be generated by the above formula. As this formula provides "good lattice points" for the integration, these nonlinear parameters can be thought to be adequate to represent the wave function in a variational approach. While the random tempering works in many examples in a superb way, one has to note that it has a serious problem: It often leads to (almost) lineaxly dependent bases. In our actual example, the best energy of Ps- with random tempering is -0.261872, and further hnprovement of this value was difficult due to the linear dependence. The parameters of the random tempering used are, in the notation of Table 4.1, ?nj 7, Tn3 5, di 4, d2 -8, d3 Tn2 4, d4

required

use

in this

=

-7, d5

=

-1, d6

The parameters

are

=

=

1, and the basis dimension nearly optimized.

-11,

di

=

p

=

=

is K

=

245.

4.2.3 Random basis

The above calculations have

suggested

that not all of the

grid points equally important grids give nearly the same energy. The explanation is simple: The basis functions are nonorthogonal to each other, none of them is indispensable; they are dense, that are

but the different

can

4. Stochastic variational method

48

will compensate any of thein can be omitted because some others for the loss. This property of the basis functions and the success of

is,

tempering suggest the idea of a completely random distribution of the parameters. To illustrate this possibility, let us generate K 100 sets of basis parameters in the expansion (4.2). The eleraents of Ak are randomly chosen from a "physical" interval: the random

=

1

1 <

0 <

10,

0 <

10,

< 20.

0 <

-\/FY23

fa13

V/a12 The

<

(4.9)

advantage of using the parametrization by aij instead of Ak 1/.\,ra-jj corresponds to the "distance' between the particles.

is that

e-l"2, the expectation value relevant to the distance is, e.g., (r) V 4/(7a), or A,/-(r-27) VF3/(2a).) The paxameters inside this interval describe the (e+e-e-) system,

(Note that,

for

a

Gaussian function

2

=

=

where the average distance between the positron and the electrons is expected to be less than 10 a.u. and the distance between the electrons is

expected to

be less than 20

a.u.

This limitation

serves

practical pur-

in pose, and it is based on the physical intuition that the paxticles bound system cannot move very fax away from each other.

The difference between the random

a

tempering and the random

distribution of the parameters is that in the former there axe several parameters which generate the parameters of the basis functions and these

optimized, whereas in functions are randomly chosen.

generating parameters

paxameters of the basis

are

the latter the

energies of different random bases are shown in Fig. 4.1. By increasing the size of the basis, the energy goes very close to the exact The

value. See Table 4.3. The energy is better than that obtained with the basis set of geometric progression type, but the comparison is diffi-

geometric progression, the matrix of nonlinear paxameters is diagonal and the partial-wave expansion is introduced to enable the trial function to span the full model space. This paxtialwave expansion increases the basis size significantly. When we use the full A matrix and randomly distribute aij, this partial-wave expansion is not necessary (see Complement 11.2). One may try to choose aij in a geometric progression, but our experience is that both the geometric progression and the random tempering of aij tend to lead to linear dependence. To avoid the linear dependence in the basis (which does not occur cult. In the

case

of the

frequently with the fully random basis), the overlap of the random basis fimctions should be smaller than a prescribed limit. Any random points which do not satisfy this condition are to be omitted and

4.2 A

practical example

49

-0.250

I -0.252-

-0.254-

Ci -0.256-

-0.258

-0.260

-0.269 20

40

60

80

100

Dimension of the basis

Fig.

4.1.

Energies of Ps- for different basis sets. The parameters of the are completely randomly chosen and no preselection is made.

basis states

Table 4.3. The energy of Ps- (in a.u.) for K basis states that are selected randomly. "Exact" energy is -0.262005. The energies Ei are obtained by

starting from different random points. The energy of "Best 100" is the one calculated by sorting the best 100 basis states from 400 basis states, where 50 random trials are probed at each step of the basis selection. Neal is the number of matrix elements evaluated during the optimization. K

=

100

K

=

200

K

=

400

Best 100

El

-0.2617619

-0.2619798

-0.2620032

-0.2619995

E2

-0.2617281

-0.2619793

-0.2620026

-0.2619978

E3

-0.2617918

-0.2619669

-0.2620016

-0.2619956

E4

-0.2618826

-0.2619675

-0.2620008

-0.2619953

E5

-0.2616285

-0.2619824

-0.2620024

-0.2619987

Nevai

5050

20100

80200

80200

4. Stochastic variational method

50

replaced by a new trial. Note that this cure cannot be applied to the procedures of the random tempering and of the geometric progression. In these procedures there is no such prescription. One can just omit some grid points depending on the actual parameters. The energies listed in Table 4.3 are surprisingly good, but the size of the basis seems larger than absolutely necessary. For the solution 400 is excessive. of a three-body problem a basis dimension of K We would like to decrease the basis size by selecting a minimal, indispensable set of basis functions. This will be described in the following =

subsections.

4.2.4

Sorting

One may wonder: Are all the basis states equally important? What happens if we omit a few states from these bases? To answer this ques-

tion,

we

reordered the basis states

by the following random selection

process: 1. A number

n

of basis states

giving the lowest energy restricted basis.

pool,

basis states, were tested in

state.

Again

2. Then

n

were

was

picked

up

randomly and

the

one

selected to be the first element of

a

again randomly chosen from the remaining a

2-dimensional calculation with the first

the state that

produced

the lowest energy

was se-

lected. 3. This

reordering

4.2.5 THal and

is continued until the last basis state.

error

search

randomly chosen nonlinear parameters give good results provided the basis dimension is big enough. For an N-particle problem, howthis ever, the basis dimension might become prohibitively large to use The

4.2 A

practical example

51

simple procedure. One can obviously improve the convergence by selecting the most important states and by not admitting all random trials in the basis set. This increase of basis dimension by searching the best among many random trials is a key of the stochastic variational method (SVM). The original procedure of the SVM, proposed in [271, has recently been developed further [281 and successfully applied to multicluster descriptions of light exotic nuclei [29, 30]. Learning from these applications to nuclear few-body problems, we have generalized and refined the method further to encompass diverse quantumfew-body systems emerging in nuclear and atomic physics

mechanical

[31, 32, 33]. The sorting method has shown that from

large number of random basis states one can select a smaller set without a significant loss of accuracy. Moreover, the accuracy can be improved by increasing the basis size. This experience motivates one to apply the following trial and error procedure, combined with an admittance test, in order to set up the most important basis set: Let Ak be the parameter set defining the kth basis function, and let us assume that the sets A,,- Ak-1 have already been selected, and the (k l)-dimensional eigenvalue problem has already been solved. The next step is the following: a

I

-

Competitive selection A number

s 1.

of different sets of

n

(Ak',

...'

Ank)

are

generated

ran-

domly. By solving the n eigenvalue problems of k-dimension, the corresponding energies (Ek,..., Ek) are determined. The parameter set Ak' that produces the lowest energy from

s2.

s3.

among the set

(El,...,Ek) k

is selected to be the kth parameter

set.

s4. Increase k to k + 1.

The essential different

motivating this strategy is the need to sample parameter sets as fast as possible. The advantage of this proreason

cedure is that it is not necessary to recompute the whole Hamiltonian matrix nor is it necessary to perform a new diagonalization at each time when

a new

parameter Ak is generated. See Theorem 3.5.

The convergence of the energy with the basis selected in this way is shown in Fig. 4.2. The convergence is much faster than in the previous case

in

number

Fig. 4.1, and n

it

of trials. The

dimensional basis sets

can

be made

even

faster

energies found by using K are

by increasing

=

shown in Tables 4.4 and

10- and K

=

the 100-

4.5, respectively.

4. Stochastic variational method

52

-0.250

-0.252

-

-0.254

Ca -0.256

-0.258

-0.260

-0.262 100

80

60

40

2-0

Dimension of the basis

Fig.

4.2.

trial and

Energies of Psprocedure

for different basis sets that

are

selected

by

the

error

Table 4.4.

Energy

of Ps-

(in a.u.) by

different

optimization strategies.

10. The energies "Exact" energy is -0.262005. The basis size is set to K Ei are obtained by staxting from five different random points. The number n denotes the random candidates probed in the trial and error procedure =

of SVM. Ne,,,,l is the number of matrix elements evaluated during the optimization. Tn the case of the full optimization by the Powell algorithm 3900

diagona,lizations were also required. The time in units of seconds is on a Digital Alpha 2100 (250MHz) workstation. The refining cycle is repeated 10 times.

Method

Powell

SVM(n=l)

SVM(n=10)

Refining(n=10)

El

-0.261251

-0.244364

-0.251083

-0.261180

E2

-0.261398

-0.234532

-0.250729

-0.261165

E3

-0.261283

-0.236207

-0.252659

-0.261040

E4

-0.261259

-0.243323

-0.252956

-0.261175

E5

-0.261193

-0.226697

-0.251260

-0.261039

N,-:.v.i

214500

55

550

88055

Time

60

0.8

1.0

11

4.2 A

Table 4.5.

Energy

of Ps-

The basis size is set to K

(in a.u.) by

=

100. In the

practical example

53

different optimization strategies. of the fiffi optimization by the

case

Powell

algorithm 7200 diagonalizations; were required. repeated only once. See also the caption of Table 4.4.

The

refining cycle

Method

Powell

SVM(n

El

-0.26200016

-0.26176191

-0.26199427

-0.26200231

E2

-0.26199947

-0.26172812

-0.26199382

-0.26200351

E3 E4

-0.26200164

-0.26179182

-0.26199733

-0.26200312

-0.26200135

-0.26188261

-0.26199778

-0.26200301

E5

-0.26200193

-0.26162811

-0.26199836

-0.26200271

Neval

35466150

11615

86150

805050

Time

7200

27

43

195

These tables also contain deterministic

procedure.

=

1)

SVM(n

10)

=

=

10)

compaxison with the performance of

a

One

can

conclude that

energy convergence with this simple selection the energy converges to the exact value.

4.2.6

Refining (n

is

a

reach

easily procedure. Moreover, one can

Refining

It is obvious that the basis size cannot be increased forever. Moreover, when the Kth basis state is

the previous states are kept fixed. This means that we try to find the optimal state with respect to previously selected basis states, but actually some of the basis states selected earlier

might

states took

not be

so

important

their role. So

succeeding procedure where the previous the following steps: over

selected,

states

are

one

anymore because the

may include

probed again

as

refining by

a

described

Refinement cycle

(A!,..., Ain)

random paxameter sets are r2. The parameters of the ith basis state ri.

generated. are replaced by

the

new

energies ElK ...Ek axe calculated. r3. If the best of the new energies is better than the original one, then replace the old parameters with the new ones, otherwise keep the candidates and the

r4.

original ones. Cycle this procedure through the

Note

that, again,

orem

3.5.

there is

no

need for

basis states from i

=

I to K.

diagonalization because

of The-

54

4. Stochastic variational method

Table 4.6.

the energy of Ps- in the refining steps. The 100 and 5 random states are probed. Atomic units are

Rnprovement of

basis size is K

=

used.

Refinement

cycle

E

(a.u.)

(Starting value)

-0.261992767

Ist

-0.262002742

2nd

-0.262003677

3rd

-0.262004063

4th

-0.262004178

5th

-0.262004255

6th

-0.262004314

7th

-0.262004339

8th

-0.262004372

10th

-0.262004398

"Exact"

-0.262005

4.2.7

Comparison

of different

optimizing strategies

4.2 A

for

a

longer time,

might get

we

practical example

somewhat better

55

energies, but the

available computer time is limited in any case. Moreover, the other methods reach at least the same energy in a fraction of this time as we

have

seen.

Tables 4.4 and 4.5 show that the full

to converge to different

indicates that the

points depending

procedure

on

optimization seems starting point, which

the

leads to different local minima. This is

by explicit inspections of the parameters. In the third column of Tables 4.4 and 4.5 the energies obtained by using different sets of completely random parameters are given. The

confirmed

next column shows the results of a trial and one

error

selection and the last

10 energy after refinement cycles. We have carried out cycles (each basis state has been cyclically probed 10 times) in

gives the

refining 10-dimensional, and

the

one

refinement

cycle

in the 100-dhnensional

case.

In summary, one may conclude that the stochastic selection of basis parameters leads to energy convergence independently of different random paths and, moreover, to very accurate results in a fraction

computational load than the full optimization. And while the latter is certainly superior in principle (one may need fewer basis states to reach a given accuracy), the former suits more practical applications. Moreover, in more complicated problems of time and

by much

less

where, in addition to the nonlinear parameters, one has to find the most adequate channels (quantum numbers, etc.) to describe the system, the random selection

seems

to be the

only

viable method. Since

the energy convergence attainable is of course not precise in a mathematical sense, one should check the quality of convergence of the wave

function

as

well.

competitive selection the steps is always admitted In the

in

the

relatively

to be

a

best candidate found

basis state

even

though

its

to be very small.

contribution to the energy may sometimes happen newly selected basis has very strong overlap with (linear combinations of) the previous basis states. To avoid this This indicates that the

an

alternative

approach called

a

utility selection [281

select the basis states. The steps go

as

can

be used to

follows:

Utility selection A. Generate

s2. Determine the

value

Ak. energyEl(k) by solving the k-dimensional eigen-

randomly

problem.

a

parameter

set

4. Stochastic variational method

56

s3. Admit the parameter set

gained by including ,El

(k)

< Ej

(k

-

it is

1)

-

Ak to be the kth element if the energy larger than a preset value Je, namely

JE.

Otherwise return to the step (sl) for the next attempt. If no parameter set was found to pass the utility test out of n consecutive

attempts, reduce JE to, say half of its original value, and to

return

(sl).

s4. Increase k to k + 1.

When competitive selection is used, convergence is inferred by the energy curve's flattening out, while when utility test is used, convergence is

signalled by

an

insistent failure to -find further elements that pass

the test. Instead of the random trial strategy described in (sl)-(s2)-(s3)-(s4) and (rl)-(r2)-(r3)-(r4), one may think of more efficient and sophisticated

approaches, like simulated annealing or genetic algorithms. approaches may give faster convergence, although the random selection strategy may have a slight advantage: It is easily implementable in a parallel way because the random trials are absolutely independent of each other. One should note that the basis elements selected by the above admittance tests are in general never optimal, not even locally. A better candidate which will gain more energy could be found in the neighborhood of the basis element admitted. The incorporation of a fine tuning, that is, an additional search for even better parameters I the vicinity of the element that passed the admittance test would clearly The latter

accelerate the energy convergence. When the evaluation of the matrix elements does not require heavy computational loads, this fine tuning is recommended to reach faster convergence. Or even a determini tic selection such as Powell's method [34, 351 might be used to find out

the

locally

4.3

best basis element.

Optimization

for excited states

The Mini-Max theorem the Hamiltonian in not

only for

Sect.

3.1)

shows that

K-dhnensional basis

ground

one

by diagonalizing

gets

an

upper bound

state but also for the excited states

happen predict the energies of the excited

may to

the

a

(see

that the basis set found for the

ground

state is

states with the

as

well. It

fairly good

same

conserved

4.3

quantum numbers

Optimization

for excited states

(angular momentum, parity etc.)

57

the

ground By optimizing only the ground state, however, the energies of the excited states will not necessarily converge (see Fig. 4.3). The energies certainly decrease because we increase the basis size, but except for as

state.

the energy of the second excited state, the upper bounds are not very accurate. (See Chap. 8 for the detail of the basis function used in the

present

section.)

0.4

171

Cd

0.3

CY)

0.2 W

0.1

0.0 0

200

400

600

dimension of the basis Convergence of the energies of the first five 'S states of the Helium atom when only the ground-state wave function is optimized. The energy difference Ej Ei'act is shown in the figure. See Table 4.7 for the exact energies.

Fig.

4.3.

-

As the ith

eigenvalue Ej

obtained

by diagonalization

is the upper

bound of the energy of the ith excited state, one may try to optimize this upper bound to get an accurate estimate for the energy of the excited state. In practice we repeat the same procedure as before, but now the basis selection is governed by the requirement that the ith

eigenvalue, get the ith

ground-state energy El, should be improved. To eigenvalue we need at least an i-dimensional basis to start not the

4. Stochastic variational method

58

with, but practical numerical considerations suggest that it is better to start with a basis in which all the lower eigenvalues (k i 1) axe already "stabld. This means that we need a first guess for the lower eigenvalues, otherwise it may happen that when improving the first excited state, for example, we pick up such components that lower the ground state. As the energies of the excited states of the Helium atom are known to a high accuracy, we will test our strategy in this case. First we 100-dimensional optimize the ground state of the He atom on a K basis. The energy of the ground state is very accurate and even the energy of the first excited state is acceptable. Starting from this K 100-dimensional basis, we increase the basis size one by one, picking up basis states which improve the energy of the first excited state. This procedure quickly improves the energy of the first excited state, while the energy of the ground state also improves a little bit (the important thing to note is that it does not get worse) because the basis size is increased. After reaching the basis size of K 200 we switch to the =

-

=

=

=

second excited state and

so on. The convergence of the result is shown th at the energy quickly converges to the exact value after its turn of optimization started.

in

Fig.

4.4. One

can see

The above

procedure gives us a basis where all the excited states are accurate up to a certain digit. We can of course create bases which give an accurate energy for an individual state, while the energy of the other states might be poor. In that case we simply carry out the stochastic search for a given state staxting from a first guess basis (like the K 100-dimensional basis in the previous case). Tbis optimization may include refinement cycles as well, if necessary. The results we obtained in this way are compared to the "exact" (i.e., the best =

calculation in the

literature)

values

[36, 37]

in Table 4.7. One

for the excited states

for the

can

t1aus

energies ground Examples of caculation of the energies of excited states win be given for the tdA molecule in Complement 8.4, the baryon spectroscopy in Chap. 9 and the four-nucleon system in Sect. 11.2. Before closing this section, we remark that the SVM assumes that the numerical accuracy of the energy calculation in each step ishigh. If the energy is calculated by, say the Monte Carlo method andhas an inherent statistical uncertainty, then the admittance test of the SVM will never work. Even when the energy is calculated by a deterministic get

as

accurate

method,

such

as a

as

state.

diagonalization, the accuracy of the numerical calgood enough to guaxantee the required precision

culations has to be

4.3

Optimization for excited

states

59

0.005

0.004

0.003 Ca >1 CD

0.002

0.001

k

0.000

400

200

0

dimension of the basis Fig.

4.4.

Convergence of the energies of the first five 'S states of the Helium one hundred basis states are selected to optimize the ground

atom. The first

state, the

next

one

hundred

(from

optimize the first excited state, and is shown in the

figure.

101 till 200) basis states are selected to so on. The energy difference Ej Eie"'t -

See Table 4.7 for the exact

energies.

Energies in atomic units of the ground state and the first four 'S excited states of the Helium atom. In column A the basis is optimized successively for all the states as described in the text (K 500). In column B the basis is optimized separately for each state, leading to five different bases (K 600) tailored for the respective states. The "exact" values are Table 4.7.

=

=

taken from

[36, 371.

State

A

B

"Exact"

EiE2 E3 E4 E5

-2.9037243758

-2.9037243769

-2-90372437698

-2.1459737740

-2.1459740452

-2.14597404605

-2-0612718887

-2.0612719880

-2.06127198974

-2-0335865085

-2.0335866779

-2.03358671702

-2.0211312479

-2.0211768312

-2.02117685157

60

4. Stochastic variational method

of the energy. An analytic evaluation of the matrix elements is thus an essential prerequisite in the SVM.

Recently an importance sampling algorithm called the stochastic diagonalization method [381 has been presented to compute the smallest eigenvalue and the corresponding eigenvector of extremely laxge matrices. It is interesting to note that though the algorithm used there has been developed independently of the SVM, it includes procedures analogous to those of SVM. The stochastic diagonalization was applied to matrices of order up to 1035 X 1035. All the above

procedures are based on the minirni a ion of the value. This is, however, not the only possibility expectation energy to find accurate energies and wave functions. As described in Sect. 3.2, the minimization of the variance of the local energy is another

possibility

in

case

will be studied in

the variance

a

can

simple example

be calculated

of the

analytically. This following Complement.

C4.1 Minimization of energy

versus

61

variance

Complements 4.1 Minimization

of energy

versus

variance

by treating a solvable m in the potential of a particle problem, an -Vo exp(-r/a) (Vo > 0). By expressing the wave function Tf V(r) as X/ /Tir, the Schr6dinger equation for this problem takes the form Here

we

compare the two ways of minimization

of mass

S-wave motion of

=

h?

d2X

-Voe'Xp I

2m dr 2

To

(-?')X=EX.

simplifT the notation, 8Tna2 VO

=

(4.10)

a

I

h2

we

and

introduce

V--8Tna

i/

2E,

(4.11)

ji2

exp(-r/2a) reduces Eq. (4.10) change of variable z differential equation of the Bessel functions

The

=

d2X Z-2 The

1 +

dX

--

z

+

dz

1,2)X (1 -Z2 _

=

to the

(4.12)

0.

boundary conditions for bound states, X(r)

=

0 at

r

=

0 and oo,

lead to the solution

X(r)

=

cJ,

( exp (_

r

with

C-2

2a

r

=f'j ( exp(-- ))2

dr,

2a

tj 0

(4.13) where the value of

J-(O

=

is determined

by

the condition

(4.14)

01

and the smallest

(4.11).

v

v

value

In order to have

gives the ground-state energy El through Eq. bound state, the potential strength VO must

a

larger than about 2.405. ground-state energy by the variational method, let us assume a simple basis function for X, rexp(-ar/a), where a is 2for a single basis a variational parameter. There is no minimum of oobtained by variance and the the function. Table 4.8 compares energy using the minimization principle for E or o-2. The parameter values 5.0, a of a are determined by the SVM. For a deeper potential of combination of two basis functions already reproduces the energy rea2.6, however, at least sonably well. For a very shallow potential of

be such that

is

To estimate the

=

=

62

Complements

Table 4.8.

Comparison of variational solutions obtained by E-minimizattion. 2-minimization for an exponential well. Units of E and o-2 are e/(8ma2) and (h2/(8ma2) )2 respectively. The mean values, (T) and and

u

,

(T 2

1/2

,

are

in unit of

with the exact

one

K

5.0

2.6

2

5

a.

is also

The

overlap integral given.

of the variational solution

E

0-2

(r)

(T2) '21

Overlap

E-min.

-3-5840

0.3236

1.4362

1.6169

0.99997

0-2_Min.

-3.5824

0.05437

1.4301

1.6044

0.99983

Exact

-3-5848

0

1.4376

1.6213

1

E-min.

-0.016446

1.275x 10-4

9.4174

12.236

0.99999

U2_min.

-0-016415

3.49Ix 10-6

9.1025

11.619

0.99940

Exact

-0.016447

0

9.4331

12.285

1

C4.1 Minimization of energy

versus

variance

63

(T2-minimization E -minimization

0

............................................... ......... ...............................................................................

i 0

10

20

wave

function-I

30

40

r1a

Fig. exact

4.5. The local energy curve for the shallow potential: wave function is also shown in an arbitrary unit.

2.6. The

5. Other methods to solve

few-body

problems

chapter we briefly show the essential points of other approaches to few-body bound-state problems. There are many different approaches and it is far beyond the scope of tbis book to discuss all of them. Included here are either only those methods which have some sort of connection with our approach or their results are frequently compared with that of SVM, and therefore a short explanation might

In this

be useful.

Quantum Monte Carlo method: The imaginary-time evo lution of a system

5.1

quantum-mechanical system is governed by the time-dependent Schr6dinger equation. When the time t is replaced by an imaginary time, -iha (a > 0), the Schr6dinger equation transforms into a diffusion-like equation The evolution of

Xf (a) aa

a

(5-1)

-HTf (a),

which has the formal solution Tf (a)

=

e-Ha Tf,

(5.2)

th-ne-independent. Here T is an initial wave function Tf (a 0). The imaginary-time evolution of the estimate the ground-state energy. The to used be function can wave

provided

that the Hamiltonian H is =

basis of this idea is Tf lim a-W

that wave

(a)-

a,

(qf- (a) I qf- (a) ) -i

is, the

wave

function at

jail

fimction a

--+

(5.3)

_

oo.

TI(a) approaches To prove

Y. Suzuki and K. Varga: LNPm 54, pp. 65 - 73, 1998 © Springer-Verlag Berlin Heidelberg 1998

this,

the exact

we

only

ground-state

need to

use

the

5. Other methods to solve

66

expansion (3.3) for TI

few-body problems

Eq. (5-2)

that a, :7 0, namely the initial wave function has a non-vanishi -n g overlap with the groundstate wave function. In what follows we assume that this condition is in

and

assume

fulfilled.

If

we

consider

imaginary

T/"(a)

time a, the

bound to the

a

variational trial function value

mean

ground-state

energy

E(a) El.

depending

on

the

of H in Tf (a)

gives an upper In fact it is easy to show t'h at

(Tf (a) I H I Tf (a)) R(a) I Tf (a))

E(a)

-2a(Ei-EI) aj 12 E+E-E ie I I i=2 1+EI i=2 e-2a(Ei-EI)JLi!J2 ai a

E' i=2 (Ei EI+

E1)e-2a(Ei-E1.) I

-

ai e -2a(Ei-El )I 1+1:' i=2 a,

ai

12

2` 12

>

(5.4)

El.

Clearly E(a) goes to E, when a goes to infinity. Another quantity called the asymptotic energy estimator is defined by 1

E(a, -r)

2T

This has the Jim

In

=

(Tf(a) I Tf (a)) (Tf(a + T) I Tf (a + -F))

(5-5)

*

following properties:

E(a, -F)

=

E(a),

(5-6)

-r--+O

+

E(a, -F)

=

E, + -In 2,r

-2a(Ei-El) e EOO I ai 12 i=2 af

(5.7)

'

e -2(a+-r) (Ei -El) I.Es! 12 J:" i=2

I+

a,

Equation (5.6) can be derived by noting that the left-hand side is equal to ( '1/2) -da.Lln(Tf (a) ITI(a)) and that the derivative can be easily calculated by Eq. (5. 1). It is clear that, for T > 0, E(a, 7) ! El and E(a, -r) converges to EI_ as a goes to infinity. In fact, the quantum Monte Carlo (QMC) method or the Green's function Monte Carlo cle to

out the

project point here is not

a

In

general,

method

ground

one

a

[40-44]

uses

state from the initial

construction of

mates the solution but

e-H'.

(GFMC)

a

good

e-Ha

wave

as a

vehi-

function. The

state space which

approxi-

calculation of the imaginary-tiTne evolution of

cannot

compute e-Ha

and H, do not commute, but

by dividing

=

e-(-ffo+H')'

the time

a

into

because rn

Ho

any smaH

Hyperspherical

5.2

steps Aa

=

a/n,

we can

(RIe-H0A'e-HIA'Ik) (RIe

-H,

IRI

=

expansion method

harmonics

approximate G(R, k)

in

=-

(RIe-"0'Ik) by

factorized form. Then the full propagator

a

ff _f G(R, Rn-1) G(Rn-1, Rn-2)

x

-

-

G(RI,k)dPfn-IdRn-2

*

..

be evaluated

use

several time steps Aa and

extrapolate

to

'

-

(5-8)

dRI

the Monte Carlo method. In

can

by

67

practice,

da

=

one

must

0 in order to

eliminate time step errors arising from the non-commuting nature of the kinetic energy and potential energy operators. the propagator (5.8) to calculate both the numerator and denominator of Eq. (5.4)

When

we use

statistical

Eq. (5.4), subject to the

E(a) a're

in

Then the nice feature

of Monte Caflo

integration. ground-state energy may be lost in method. One of the most serious problems in the QMC is the so-called minus-sign problem [43, 451. The propagator G(R, k) is not always positive. This makes it difficult to use importance sampling techniques based on the classical stochastic process such as a Maxkov process or a Molecular Dynamics technique in computing the propagator by the Monte Carlo method. of

having the QMC

an

upper bound to the

Hyperspherical

5.2 We

errors

briefly

introduce

an

harmonics

approach

expansion

which is based

on

method

the

the trial function in terms of hyperspherical harmonic

expansion of

(HH)

functions.

spherical harmonics are useful to expand the angular funca single-particle motion, the basic idea of the HH method is to generalize this simplicity to a system of particles by introducing a global length p called the hyperradius and a set of angles Q. Let us suppose that all of the particles oscillate harmonically with angular frequency w Just

as

the

tion of

N

N

2

Pi

HHO

rniw2Ir2

+

Using

the Jacobi coordinate set,

one can

into the intrinsic and center-of-mass N-I

1 +

2yi

_2

separate the Hamiltonian

parts

N-1

7r2

HHO

(5.9)

2

2mi

/-Ziw2X2i +

7r2N 2rn12

...

2

N+ 2 'rn12---NWXNi (5.10)

5. Other methods to solve

68

few-body problems

where Ai is defined by Eq. (2.19). Among the 3(N 1) degrees of freedom for the intrinsic motion, -

the

p is defined

hyperradius

by

N-I 2

[lix?

P

(5.11)

The

hyperradius contains only intrinsic coordinates, but it can also expressed as E i_=, Mi(Ti XN )21A, which is proportional to the moment of inertia of the system (see Eq. (2.18)). The choice of IL can be axbitrary, The hyperradius is apparently symmetric with respect to the interchange of particle labels. The potential energy of the intrinsic 2P2. Just as the single-particle kinetic part is simply expressed as -Ilzw 2 radial and angular parts, the intrinsic is into separated energy operator be

-

kinetic energy operator is reduced N-1

h2

7r2

I: 21.Lii

2jL

i=1

02

[5;;72

3N

-

as

follows

4 0

+

L

-ap

P

2

(5.12)

p2

where L is called the

grand angular momentum, which is expressible in terms of 3N 4 angles S2. there is no unique way to choose the angles, one possiAlthough bility is to choose 2(N 1) angles &j and 0j, the polar coordinate of N k 1, 1) and the other N 2 angles -yk (0 < -yk E, xi (i 2 2,3,..., N 1) called the hyperangles as follows -

-

=

-

-

...,

-

-VFILIV-1 XN-I V Ak Xk ,//-Ll x,

=

=

=

V/jL P COS7N-1,

- ,FA P Sin7N-1

Vrj-Lpsin-yjv-j

...

...

Then L is related to the usual

(k

Sin'Yk+1COS7k

angular

momentum

LN-D

a2

2

Lk

3(k

-

2

a7k

-

2)cot-yk

Lk-I +

+ COS

'Yk

sin -YA;

...,

N

-

+

(k

4cot2-yk

2,

2), (5.13)

2

=

2,

siny3sint2.

follows

L2

=

la-lk

N

2),

1k

=

"Xk h

X

-irk

as

5.2 2

L1

The

Hyperspherical

harmonics

expansion method

=121.

69

(5-14) of L 2, called the HH

eigenfunctions L 2y/C (S?)

=

K(K + 3N

-

functions,

5) Yjc (Q)

(5.15)

by the quantum number )C which comprises K (K 5 eigenvalues of the angular operators. 0, 1, ...) Expressing the intrinsic wave function as a sum, over k, of products are

chaxacterized and 3N

-

of radial functions

RK(p)

and the HH functions

Y)c(Q),

3N-4

Ep-

-V

(5-16)

RIC (P) Yk

2

/C

N-body Schr8dinger equation, after eliminating the center-of-mass motion, is reduced to the matrix equation for the radial functions the

d2

'C(C + 1) P2

(_W [ dp2 21L

E)

(p)

N

+

1: (YK 11:

Vii I yic) RIC, (P)

=

0,

(5-17)

with

L=K+

3(N 2

-

(5.18)

2).

The volume element is

given by

N-i

P3N 4dpdQj

fj dxi

MIL2,

AN-I

N-1 x

fj df2kSin3k-4,YkCoS2,YkdYk,

(5-19)

k=2

df?k Sin?ykd'OkdOk is the usual surface element. Because C is positive for N > 3-particle systems, it turns out that the "centrifugal baxrier" is always present in N > 3-particle systems even for zero total

where

orbital

=

angular

For the HH ation of the over one

momentum states.

expansion method to be practical, of course, the evalu-

potential

has to have

energy matrix elements must be feasible. Moreguide for the truncation of the HH basis, even

a

5. Other methods to solve

70

few-body problems

the

expansion converges with a few K values, because the deof the HH functions is high. It is also necessaxy to construct generacy the HH functions of proper symmetry for a system of identical par-

though

ticles. This is

a

difficult

HH

expansion method

(N

<

5).

A

sophisticated

a

to

with FT. In

it limits the

application of the systems of rather small numbers of particles

version of the HH

correlation factor F

(5.16)

problem, and

expansion method [461 employs

N

=

[36,

113'>i=l hi

ri

-

rj) [471, replacing

TV in

481 the correlation factor is chosen to

Eq. satisf ,

special boundary condition like the cusp condition for the Coulombic system. (See Complement 8.1 for the cusp condition.) The use of the correlation factor accelerates the convergence and leads to precise a

solutions. The HH expansion method was introduced in 1935 by Zernike and Brinkman and reintroduced 25 years later by Delves and Smith. See

for

example [49, 50]

for details and

[511

for recent

developments.

5.3 Faddeev method

T

=

'01

+

V)2

+

(5.20)

?P31

where for the bound state each component is related to Tf

*j

GoViTf,

=

where the free

or

(E -110)0i

three-body propagator

=

is

by

(5.21)

ViTf, given by

I

Go

-

E Here

Ho

-

is the

netic energy

-

Ho' three-body kinetic

being

(5.22)

energy with the center-of-mass -kisubtracted. The potential Vi is expressed in terms,

5.3 Faddeev method

V12 It V23 V2 V31 V3 notation, that is, V1 is easy to see that Eqs. (5.20)-(5.22) is equivalent to the Schrbdi-nger HO + VI + V2 + V3 equation (E H) Tl'= 0 with H We show two forms of the Faddeev equations which are widely of "odd

man

out"

71

: --

:::--

i

-

i

=

-

used for numerical solutions. One is the differential form which results

by rewriting the

(E

(E (E

-

Ho

-

-

Ho

-

-

Ho

-

Another is the

Oi

=

second form in

Eq. (5.21):

VI),01

=

V1 (02

+

03)

V2)02

=

V2 (03

+

01)

V3)7P3

=

V3 (01

+

02)

integral

(5.23)

form of the above

(j 7 ij

GiVi(Oj + Ok)

k

equation

=7 i, j :7 k),

(5.24)

with

Gi The

(5.25)

=

E

integral

-

Ho

form

-

Vi'

can

G,

02 03

be

simply expressed 0

0

0

G2

0

0

0

G3

in

matrix form

a

0

V,

Vi

V2 V3

0

V,2

V3

0

'01 2

03

(5.26) satisfy the boundary condition that Oi large distances. This condition is, a particular value of energy E, which is notbing but the energy eigenvalue of the three-body system. The Faddeev method is thus a direct method to solve the eigenvalue problem. It does not rely on the variational principle. There are three possible choices for the Jacobi coordinates X(1), X(2)7 X(3). See The bound-state solution has to all of the components however, met only for

Fig.

vanish at

2.2. It is natural to express the Faddeev

of x(l), and likewise

02 by X(2) and 03 by X(3)

component 01 in .

The most difficult part

in numerical works of the Faddeev method then

comes

uation of matrix elements between the functions

of the different Jacobi coordinate sets. Readers for

some

details for nuclear and Coulombic

problems. In Chap.

11

we

will show that

related Gaussians with the

use

a

are

from the eval-

expressed

in terms

referred to

three-body

[55, 561

bound-state

optimization of the corSVM gives solutions that are

careful

of the

terms

5. Other methods to solve

72

few-body problems

in excellent agreement with the results of the Faddeev method for

nuclear

three-body problems.

A real power of the Faddeev method is

probably not only in boundstate problems but in applications to scattering and continuum problems. See [541 for the recent developments on this subject. It is possible to extend the Faddeev method to four-particle system. The Faddeev equations are then called Faddeev-Yakubovsky equations which consist of seven components, four for I + 3-partition of four particles and three for 2 + 2-partition. Numerical solutions become increasingly difficult.

5.4 The

generator coordinate method

There is

a

which is

a

called the generator coordinate method (GCM), natural extension of Eq. (3.7) to the case of continuous

theory

superpositions. The GCM is a powerful method and has a variety of applications such as the restoration of symmetries or good quantum numbers (e.g., angular momentum and particle number) In many-body wave functions, the microscopic description of reaction dynamics between two composite particles and collective motions of many-body systems. The GCM

assumes

that the trial function is

a

continuous superpo-

sition of the basis function Tf (a), which is often called the

generating

function: Tf

=

f f (a)

Tf (a) da.

(5.27)

f (a) is called a weight function. A real or complex parameter a specifies the generating function. It is called the generator coordinate to distinguish it from a physical coordinate. The symbol The function

a

may

tegral

represent in

more

Eq. (5.27)

than

is then

one a

parameter:

the

equation known

principle as

=

multidimensional

the parameters. The choice of the important in the GCM. The variational

a

generating

a2l

...

).

integration

is used to determine

f H(a, a')f(a)da' El B(a, a')f (d)da', with

,

functions

the Hill-Wheeler equation

=

(al

f (a)

Tf(a)

The inover

all

is most

and leads to

[571 (5.28)

5.4 The generator coordinate method

(a, a) Here

=

li(a, a)

(Tf (a) I H I Tf (a)), and

13(a, a')

B (a,

are

the Hamiltonian kernel and the

a)

=

(Tf (a) I Tf (a)).

73

(5.29)

linear integral operators and called

overlap (or norm) kernel, respectively.

the GCM looks very similar to the diagonalization of the Hamiltonian in the basis states TV (a). This is true if the parameter a

Formally

is discretized and if

only a finite number

of functions Tf (al) ,

...

i

Tf(aK)

are used. Then the HiU-Wheeler equation reduces to the generalized eigenvalue problem (3.10). For further details see [57-601. Examples

of

using discretized generator

10.4.

coordinates

are

given

in Sects. 8.4 and

6. Variational trial functions

Due

care

of the correlation between the

particles

is

important

for

a

precise variational solution. The variational trial functions used in this text, correlated Gaussians and correlated Gaussian-type geminals, are formulated

by using a generating function g. Orbital functions with arbitrary angular momenta or Cartesian polynomials around arbitrary centers are constructed from g by using a simple, well-defined prescription. It is also shown that the generating function can be related to the product of single-particle Gaussian wave-packets through an integral transformation. This 'uncorrelated' form is useful to extend to a many-body system of identical particles. The spin function for an N-fermion system is briefly discussed.

6.1 Correlated Gaussians and correlated

Gaussian-type geminals approach is the choice of the trial function. To solve an N-particle problem, it is of prime importance to describe the correlation between the particles properly. The correlation between the particles can be described by functions of appropriate relative coordinates. The correlation is then conveniently represented by a correlation factor, F rl3',,i=, fij (ri rj). There are two widely applied strategies: (1) One is to use this form of F directly by selecting the most appropriate functional form to describe the short-range as well as long-range correlations. Such calculations are, however, fairly involved for systems of more than three particles and the integrations involved require the Monte Carlo technique. (2) An alternative way to incorporate the correlation is to approximate fij by a number, possibly a large number, of simple terms which facilitate the analytical calculation of the matrix elements. We follow the second course by using an expansion over a correlated Gaussian "basis". Most crucial for the variational

=

Y. Suzuki and K. Varga: LNPm 54, pp. 75 - 122, 1998 © Springer-Verlag Berlin Heidelberg 1998

-

6. Variational trial functions

76

important that two basic requirements axe satisfied in the second course. First, in the limit of large dimensions the basis functions should become complete, so that the results obtained by means of some systematic increase of the number of basis functions could converge to the exact eigenvalue. Second, for the approach to be practicable, computational effectiveness is required for the basis functions. The It is

matrix elements have to be evaluated with ease; otherwise calculations witli combinations of a great number of basis functions would be

extremely difficult. In our opinion only the correlated Gaussian basis meets these requirements. The usefulness of Gaussians was already suggested in 1960 independently by Boys [611 and Singer [621, and since then exploited by many authors [63, 22, 64, 65, 661. Though a mathematically sound proof may not be available for the completeness of the Gaussian functions, a heuristic argument for it is possible as follows: As is discussed in Complement 6.1, any square-integrable, well-behaved function with angular momentum 1m can be approximated, to any desired accuracy, by a linear combination of nodeless harmonic-oscillator functions eter

a

(Gaussians)

(Eq. (6.37)). By generalizing

N-particle

continuous size paramthis to the N-particle system, the

basis function then contains

N

rj)21

F=

(r113" ,,j=jexpf--!a-2

This

simple correlated Gaussian

U

calculations. For

a

specific

for

cases,

see

-

?,

discussion

is

on

of

=

a

a

product

eXpj

-.1 2

of these Gaussians:

EN )2j. j>i=l ozij(ri -,rj

actually widely used in variational the completeness of Gaussians for

example [67, 351.

Of course, we have to keep in mind that the Gaussian is not economical in describing the asymptotic behavior of the wave function at

laxge

distances

(see Fig. 6-2). Moreover,

it does not

predict

a

correct

specific quantities such as the cusp ratio. See Comasymptotics and the cusp ratio could be well plement described with exponential functions. For example, welinow that the Rylleraas-type functions give very accurate results for Coulombic fewbody system (see, e.g. [68, 691). The correlated exponential functions are not, however, amenable to analytic evaluation of matrix elements for a system of more than three paxticles. This makes it difficult to use the exponential functions as a vahational trial function for a general N-particle system. value for

some

8.1. Both the

We extend the above argument further to define the correlated we consider separately two cases for two types

Gaussians. For this

of Hamiltonians. First in be

expressed

hn

terms of

case a

of

set of

Eq. (2.1) the Hamiltonian can independent relative coordinates

6.1 Correlated Gaussians and correlated

,7

x

(xi,

=

...

,

xN-1).

As

was

shown in

Gaussian-type geminals

Eqs. (2.23)-(2.25),

77

it is then

con-

venient to express F in terms of x, instead of N(IV- 1) /2

interparticlefunction, a so-called

distance vectors, ri rj. An N-particle basis correlated Gaussian, then looks like -

I:

Type where A is

TI

(N

an

exp

=

-

1)

(_2 :TbAx)

x

(N

0 (x),

(6-1)

1) positive-definite, symmetric

-

matrix

of nonlinear parameters, specific to each basis element. As mentioned in Sect. 2.2, the matrix A with these properties can in general be written

6DG with the use of an orthogonal matrix G and a diagonal

as

matrix D with all

positive diagonal elements. The function O(x) is a generalization spherical harmonics Y of Eq. (6.56) to the many-particle case. More details will be given below. of the solid

The second each

is

is suited to the Hamiltonian

case

governed by both

(2.2).

The motion of

the

single-particle potential and the two-body Eq. (6.1) to include an independent motion of the ith paxticle around some point R, Here PI, is not a dynamical coordinate but just a parameter vector. In this particle

interaction. It is thus useful to extend

case we

but

do not need to

can use

the

use

the relative and center-of-mass coordinates

single-particle coordinates. Therefore we are led to

the

following type of correlated Gaussians which are often called correlated Gaussian-type geminals N

expf

XeXpf Here

r

-

aij (,ri

-

2

-

2

Y

R stands for

i(ri a

N

E j>i=, aj(,r, _,rj)2 A defined N

3=i+l

can

through Aij as

Type

11

:

Tf

=

x

Ri

)210(,r

be written

=

exp

-

T3)2

set of vectors

aij, the correlated

expressed

_

Aji

=

firl

R). RI,

-

compactly

-aij

(i

<

as

-

R),

Ar

-

2

(r

-

---,,rN

-

Ar with

j), Aii

Gaussian-type geminals

1 -2

O(r

_

=

can

R)B(r

-

RNJ_ a

matrix

E''-=, aji

in

R)

As

general

+

be

I (6.2)

78

6. Variational trial functions

6.1 Correlated Gaussians and correlated

Gaussian-type geminals

79

optimization of nonlinear parameters allows us to obtain high-quality solutions with expansions containing not too many terms. The Gaussian of type I is a special case of type IL To unify the description for both cases, we change the notation in what follows throughout this chapter according to the following conventions: As it is cumbersome to use x or r depending on the type of problems, we in the

of the presence of an external field. To have N as the number of xi coordinates in both cases, we consider (N + 1) particles for the basis of type I and N particles for the basis of type II,

will

use x even

respectively.

case

Table 6.1 summarizes

our

conventions for the notations.

Table 6.1. Convention of the coordinates jo

`:

(XII X21

---I

XN)

in the

cor-

related Gaussians and the correlated are

abbreviations of

Number of

Meaning

Gaussian-type geminals. SP and CM 'single-particle' and 'center-of-mass', respectively.

particles

of

x

T ansformation matrix

from SP coordinates

SP coordinates relative -

ri

Gaussian-type geminals (Type II)

N+I

N

Relative coordinates U: Ur X =

SP coordinates U=1:

X=r

IV

I

XN+1

Ei==1 mixi

7nl2---N

(U-1X)i

Xi

-

XCM

XCM

Relative distance vector -

Correlated

(Type I)

r

CM coordinate: xcm

to CM: ri

Correlated Gaussians

(U-I-X)i

-

(U-'x)j

Xi

-

Xj

rj

Before

discussing the

function

O(x)

in

Eq. (6.1)

we

distinguish two

types of variational calculations: One is a type of calculation called a vaTiation before projection. Here the trial function used is not neces-

sarily an eigenstate of some of the conserved quantities belonging to the symmetries of the Hamiltonian such as paxity and angular momentum. After the variational calculation, the conserved quantities are proje-ted out from the trial function. For example, we know that an eigenstate of a rotationally invariant Hamiltonian should have a good angular momentum. Yet one often uses a variational trial function that does not have the proper rotational symmetry but, after the

6. Vaxiational trial functions

80

variational calculation, the symmetry is restored by angular momentum projection. The restoration of good angular momentum is ensured

superposition of the rotated variational solutions and the weight function involved in the superposition can be determined, e.g., by the

by

a

generator coordinate method of Sect. 5.4. Another type of calculation

after projection, where the trial function

is what is called variation

constructed

so as

is

quantum numbers of the conthe variation after projection is superior to

not to mix different

served quantities. Clearly the variation before projection because the variation in the former

case

only in the state space which has the same symmetry as solution, while in the latter the variational solution tends to reach a minimum in the space including the basis states with different quantum numbers. Even a calculation of variation before projection type, if thoroughly done, would reach a solution that has the proper symmetry in the limit that the state space is complete. See Sect. 10.4. Of course calculations of the variation after projection type become more challenging because it is in general not easy to calculate matrix elements with trial functions that are eigenstates of the conserved observables. Our objective is, however, to use trial functions with the

is carried out

the exact

proper symmetry. The function O(x) in

Eq. (6.1) describes non-spherical motion. To angular momentum L and its projection M, a direct generalization of solid spherical harmonics Y (4.5) (see Complement 6.2) to a many-particle case is a vector-coupled product of the solid spherical harmonics of the relative coordinates: describe the orbital motion with the orbital

[[[Yi, (XI)

OLM*

X

)(

...

Y12 (X2)IL12

X

Y1' *V)

I

X

Y13 (X3)IL123

LM

N

C.

r-=JM1.IM27 where c,, is

a

...

(6.3)

Ylimi (xi),

7MNI

product, (IIM112M2 IL12 M1+M2) (L12 M1+M2 13M3 IL123

M1 +Tn2 +M3)

-

-

-

(L12 N-IMI+?n2+-+TnN-1INmNJLM),

of the

...

Clebsch-Gordan coefficients needed to couple the orbital angular mospecified quantum numbers. Here each relative motion

inenta tG0 the

has

a

angular momentum. See, e.g., [2, 70, 71, 721 for the deangular momentum algebra. Angular momentum recoupling

definite

tails of

coefficients used in t'his book will be defined in

Complement

6.3.

6.1 Correlated Gaussians and correlated

Gaussian-type geminals

81

Since the

angular momentum of the relative motion is not a conquantity, it may be important for a realistic description to include several sets of angular momenta (117 12 IN; L12, L123 ) This is the case especially in nuclear few-body problems [32, 251 because the non-central components of the nuclear potential necessitate higher partial waves. For example the tensor force couples S waves to D waves. It is also noted that a faster convergence is in general obtained by allowing the use of different sets of relative coordinates together with suitable sets of angular momenta [30, 20, 251, because a parserved

7 ....

i

...

-

ticula,r type of correlations can be best described in the coordinate set conforming to the type of correlation. From the fact that OLM(X) can

be

expressed by

different

paxtial-wave decompositions

in different

relative coordinate systems, one can conclude that the use of partial waves may not be so important after all. Besides, the various possible

partial wave contributions

increase the basis dimension.

calculation of matrix elements for this choice Of OLm (x) becomes too

Moreover, sooner or

This choice is therefore

complicated. especially as the number

the

later

obviously particles increases and/or different sets of relative coordinates are employed. This difficulty can be avoided by adopting a different generalization of Y for OLM(x) [33, 311: nient

OLM(X)

inconve-

of

V2KYLM(V) N V 2K+LyLob)

Only

the total orbital

number in most

cases

pression. The real

with

v

Uixi

which is

angular momentum,

(at

vector ii

a

=

fix.

(6.4)

good quantum

least =

approximately), appears in this ex(ul,..., uAr) defines a global vector, v, a

linear combination of the relative

coordinates, and the wave function angle b. The vector u may be

of the system is expanded in terms of its considered a variational parameter and

one

may

try

to minimize the

energy functional with respect to it. The energy minimization then amounts to finding the most suitable angle or a linear combination

of

angles.

The

of the parameter u can be more advantavariational calculation than the discrete nature of the set of

continuity

geous in a the angular momenta

(111 12

IN; L12, L123 -) because the change of the energy functional can be continuously seen in the former case. The factor of v2K+L plays an important role in improving the short-range 7 ...,

i

.

behavior of the basis function. A remarkable

advantage

of this form

6. Variational trial fimetions

82

of

is that the calculation of matrix elements becomes much

OLm(x)

simpler

than in the former

momenta is

completely

case

coupling of N angular appendix for details.

because the

avoided. See the

Eq. (6.2) the construction of the trial function with good orbital angular momentum may not be an For the function

0(,r

-

R)

in

immediate concern, because the vector R is intended to determine a specific shape of the system. The function 0(r R) is chosen in the -

spherical

basis

as

N

O(x or

-

R)

_nz.12kiy1 imi (X,

IX,

in the Cartesian basis N

0 (x

-

i=1

(6-5)

IZZ

as

3

fl 11 (xip

R)

_

-

(6-6)

Rip)nip,

P=I

where the index p = 1, 2, 3 stands for x, y, z components of the vectors xi and R, and nip is a non-negative integer for the p-direction of the

simple transformation for the polynomial parts between the spherical basis and the Cartesian basis, the above two representations are actually equivalent. See Complement 6.2. In the following we assume that 0 is given by Eqs. (6.3) or (6.4) for the correlated Gaussian of type I and by Eq. (6.5) or Eq. (6-6) for the correlated Gaussian-type geminal of type II. The Gaussians of type I have definite parity of either ith

or

particle.

Because there is

a

(_l)L, depending on the choice Of OLM(X),

type II

parity

are

not

while the Gaussians of

eigenstates of the parity operator. To project out good function, one has to take a combination of two

from the trial

Gaussians with the centers at R and -R.

6.2 Orbital functions with

arbitrary angular

momentum The construction of

a

trial function with

good angular

momentum

is very important for obtaining solutions of a rotationally invariant Hamiltonian. In the previous section we introduced the forms of

OLM(X) Since

to describe the orbital fimction with

Eq. (6.3)

good angular momentlan. Eq. (6.4) takes

appears to be better established but

6.2 Orbital functions with

arbitrary angular

momentum

83

particularly simple form and makes the calculation of matrix elements very simple, it is useful to understand the relationship between the two angular functions. a

Any functions of type

Theorem 6. 1.

N

v2KyLM (V) can

be

with

expressed

2ki

2k2

-

-

all

*

*

X

*

X

Y12 (X2)] L12

YIN

of terms

Y13 (X3)] L123

X

(XN)l LM7

non-negative and satisfy 2k,

+

11 + 2k2 +12 +

-+2kv+IN =2K+L.

Proof. We V

are

linear combination

a

[[[Yl (XI) X

where ki and li

uixi

of

in terms

x2k'

X2

XI

v

=

prove the theorem

by induction.

For

U1XI + U2X2, the assertion is true because

equality [73, 747 75] (see Exercise

6.1 for

v2KYLM(V)

D

a

a

we

two-variable vector know the

following

simple proof):

KL

kj.Ijk212

U2k3-+llU2k2+12 2 1

2kl.+11+2k2+12=2K+L

XX

where

DKL

kjIjk212

DKL kjIjk212

-

-

is

-

[Y11 (X1)

same

Y12 (X2

LM7

Bkj.,,Bk2l2 (2K + L)! Q1112; L). BKL (2k, + I,)! (2k2 +12)1

(6.7)

(6.8)

by

47r(2k + 1)! 2kk!(2k + 21 + 1)!!'

and C is the coefficient needed to

the

X

given by

Here Bkj is defined

BkI

2klX2k2 2 1

(6.9) couple two spherical haxmonics with

argument [70]:

1YI 00

X

and reads

as

YI'001 LM

=

C(Il; L) YLm (i),

(6.10)

6. Variational trial fimetions

84

1 +::1: (21+1)(211+1) L (101'OILO). 4 4v(2L 47(2 v(2 + 1)

F2

Qll'; L)

The coefficient C vanishes unless I + I' + L is For

general

a

of the vector

case

VN-1 +UNXN With VN-1

vector-coupled products and

x

U1X1 +

=

V2KyLM(V)

formula to show that

2kN

v *

*

even.

-,LulvxN , we put v +UN-lXN-1 and use the above ulxl +

=

*

(6.11)

can

be

*

-

expressed 2K12

of the terms of

v

...

N-1

1

in terms of the

YL12

...

(VN-1)

Y1N (XIV) with 2K12 m-1 + L12 N-I 2K + L 2kN 1Ndecomposing VN-1 to VN-2 + UN-IXN-I, one can apply =

N

N-I

...

By

further

the

same

2KI2 N-1 to vN-1 YL12 Then it is clear that we ...

argument

repeatedly.

-

-

...

...

N-1

can

(VN-1)

th is process show that the statement is and

use

true.

Theorem 6.2. A

two solid

vector-coupled function of

spherical

harmonies

[Y11 (Xl) be

can

X

(X2)]

Y12

expressed

(-1)11+12

with

=

(_I)L

LM

in terms

of a

linear combination

of terms

X2ki.x2k2V2qyLM(V), 2 1 where

2k, + 2k2 the- form Of V =

Proof.

For

a

2q

+

=

(6.12) 11

+

UIXI + U2X2

L

given

L and the vector

of each term has with appropriate coefficients ul and U2

12

value, 11

-

v

-

+

12

-

L is

even

and non-negative, and

thus 11 + 12 may be set equal to 2k + L with a non-negative integer k. We use induction with respect to k. First we show that the statement is true for k 0 (11 + 12 L). As Eq. (6.7) shows, for the K = 0 =

case

there

are

=

with

(see also Eq. (6. 108)), and (L + 1) terms of [YI(xi) x By taIdng (L + L), each multiplied by UI1 UL-1. 2 L with + + X2 (i aix, 1) ai =7 0, we

only terms

k,

=

k2

=

0

V

=

UIXI + U2X2 consists of

YL-I (X2)] LM (I

=

0,

YLM(V)

With

...,

1) different vectors, vi obtain

=

L

YLm(vi)

=

-21+

71 + 1)! 4-Ax(2L 1. 21 + I)! 1 1+ 1) (2L

E(aj)' 1=0

X

One

can

[YI(XI)

view the above

equations for [Yl(Xl)

X

X

-

YL-1(X2)]LM-

equation as

a

(6.13)

system of simultaneous linear

YL-I(X2)]LM (multiplied by

the square root

6.2 Orbital functions with

arbitrary angular

factor).

The determinant of

nothing

but Vandermonde's determinant and it becomes

(L + 1)

(L + 1)

x

85

momentum

(ail)

coefficient matrix

nonzero

is

for

different

ai's. Therefore the solution of the linear equation exists, and hence it is possible to express [YI (XI) X YL-1 (X2)] Lm as a combination of terms of YLm(vi). Thus our assertion has been proved. Next we assume that the statement holds for k < K 1, and will show that it also holds for k K. To prove this, we note that a general [YII (XI) X Y12 (X2) I LM With 11 + 12 2k + L 2K + L which satisfies the triangular relation Ill -121 :! L < 11 +12 takes the form [YK+l (xi) x YK+L-1 (X2)] LM (1 0, L). What we have to show is that the term -

=

=

=

=

...,

[YK+1(Xl)

YK+L-I(X2)]LM is expressible as a combination of terms of the form of Eq. (6.12). Now, looking at Eq. (6.7) in its full generality, the expansion of V2KyLM(V) contains all of these (L + 1) functions, each

X

multiplied by

u

K+I u

K+L-1

2kt+li

and

further terms. These have

some

the form const. x u 1

2+12X 2kjX2k2 lyll (XI) 1 2

at least

nonzero

one

U2 of k, and k2 is

+ L with k

k2)

=

K

-

ki

k2

-

< K

Y12(X2)ILM

in these terms

appropriate

v

are

k,

-

1.

-

Equation (6.7)

vectors.

where -

Thus, by the assumption that 1, all factors [YI, (xi) x expressible in the form of Eq. (6.12) -

statement of the theorem holds for k < K

with

Y12 (X2)]LM7 equal to 2 (K

X

and 11 + 12 is

can now

be rewritten

as

L

E

V2KyLM(V)

u

K+L-1

K+1

U2

1

CKLI [YK+l

(X1) X YK+L-1 (X2)ILM

1=0

+

(6.14)

...'

where CKLI is a suitable constant factor and the symbol indicates the terms that axe already expressed in the form of Eq. (6.12) as stated above. in

exactly

By taking (L

the

+

different vectors vi in V2KyLM(V) before, Eq. (6.14) can be viewed as

1)

same manner as

system of lineax equations for [YK+I(XI) X YK+L-1(X2))LM, which is also solvable. The solution yields [YK+I(XI) X YK+L-I(X2)lLm as a

combinations of terms of is clear from the

uniquely

proof,

Eq. (6.12).

note that the

completes the proof. As vector v in Eq. (6.12) is not

This

determined.

It is easy to see that the following result.

repeated application

Theorern 6.3. A vector-coup led product

of Theorem 6.2 leads to

of solid spherical haT7non-

ics

[[[Yll-(Xl)

X

Yl,2(X2)IL12

X

Y13 (X3)IL123

X

X

YIN (XAr)lrm

6. Variational trial functions

86

(-1)11+12, (_j)L123 (_l)L12 (_I)Ll2 N-I+IN can be expressed in

With

=

...

(_I)L12+13,

=

...,

(_ 1) L

and

of a linear combination of

terms

terms N

I

(Xi Xj) kjj V2qyLM(V) -

with 2

of each Uj's.

li i= Ei> j=1 kij + 2q X:N is given by EN 1 UiXi With

kii

j=1

term

+2

=

v

Since the factors roles in lish the

-

1

xj2

=

(xi xj)

and

-

are

L, where the

pprop,riate.

a

vector

co

scalar, they play

v

j cient8

no

active

the rotational motion. Theorems 6.1 and 6.3 estab-

desci ibing equivalence

between the

angular

Eqs. (6.3) and angular momenta a-Te the parity oL the basis

functions of

(6.4)

under the condition that the intermediate

restricted

stated in Theorem 6.3 and that

as

L

given by (_ 1) through the angular momentum L. The basis function whose parity is given by (_l)L is called tohave a natural parityThe construction of a general angular function with unna ural parity must be based on the vector-coupled form of Eq. (6.3). Unfortunately there is no simple function analogous to Eq. (6.4) for the unnatural parity case. One way to construct the angulax function with unnatural parity is for L > 1 function is

OLM (X)

V2K [YL-1(V)

.

X

W]LM

with v

=

iix

and

Sij (xi

w

x

(6.16)

xj),

skew-symmetric matrix which satisfies Sij 0-, YL-I(v) must be replaced -Sji. For the special case of LI with YI(v). A slightly simpler angular function would be possible by introducing another vector v' as follows:

where S is

an

N

x

N

=

OLM(X)

=

V2K [YL(V)

X

VILM)

Vr

=

I?X-

(6-17)

Eq. (6.7) that in the case of K 0 both ki and k-2 are limited to zero and only the stretched coupling, namely 11 + 12 L, is allowed. See Exercise 6.1. With an increasing K value the possible values of partial waves 11 and 12 increase including the case of nonWe note in

=

=

stretched

coupling.

This

applies

to the

case

of many variables

as

well.

6.3

To increase K is thus

one

way to include

Generating ftmction

higher partial

waves

87

in the

calculation. The matrix A of the correlated Gaussian is often assumed to be

diagonal in order

In this

case

to reduce the number of nonlinear

parameters.

has to increase K when the contribution of

one

high

important. However, in the case where expected partial A is not diagonal, additional and important partial-wave contributions come from the cross terms of the exponential part of the correlated 0. E.g., the term exp(-Aijxi xj), when Gaussian even with K expanded into power series, contains many terms of the form (X,.X,)n, which can describe high partial waves associated with the coordinates relation xi and xj. This is easily understood by noting the following to be

is

waves

-

=

for

arbitrary

vectors

(a .,r)n

a

and b:

Bkja

2k

r2k

2k+l=n

E

Yj,,,(a)*Yj,,,(r) M=-1

Bkja 2kr 2k(_1)1,,

F21-+l[Yl(a)xYl(r)loo, (6.18)

2k+l=n

Eq. (6.45) and the addition theorem (6.54) for spherical harmonics. This implies that even the basis function with 0 is expected to be useful if a general matrix A is used in the K variational calculation. The calculation for the dtl-L molecule given in Complement 8.4 will clarify the point discussed in this paragraph.

which results from

=

6.3

Generating function

The calculation of the matrix elements becomes

generating

function for the correlated Gaussian.

simpler if one uses a In fact, the following

function g, which contains an auxiliary "vector" A (8 1, ..., SV), is found to generate the correlated Gaussians of both type I and type 11 =

conveniently:

g(s; A, x)

=

exp

To relate the use

the

following

(-2 ;Mx 9x).

(6.19)

+

generating

function g to the correlated Gaussian

formula

B kja2k+l r 2ky1M (,r)

=

fYjm (ol) (a

.

r

)2k+lda

we

6. Variational trial functions

88

f Y,.(

=

,

(

92k+l

Aa-r

dal

e

a)

OA2k+l

(6.20)

A=O

which is

easily proved by using Eq. (6.18). Then the vector-coupled product (6.3) can be generated from the factor egx of the function g as follows: By choosing si aiti with a unit vector ti we obtain =

N

-I bAx)

exp

YI,., (xi)

2

dii- Y ,,., (Fi)

B01i

Oai

g(a It; A, x)

(6.21) By a symbol alt we mean a "vector" such that given by aiti, where & (a, aiv) with ai =

I

(ti,

...,

tN)

is

I

a

The

x

N

-

- -

one-row

7

each component is a real number and

matrix of Cartesian vectors ti.

in the above

key point equation is Eq. (6.20) which relates the solid spherical harinonics to e ". Since Eq. (6.20) yields a more general term r2kyl., (,r) than just the solid spherical harmonics, it may also be useful to use a simpler relation, which generates just the solid spherical haxmonics. The relation (6.58) serves for this purpose. By choosing tj (1 T,j 2, i(I +,ri 2), -27-j) (j 1, N), we obtain =

=

...,

IV

exp

2

TbAx)

Y1,m, (xi)

N

a Ii-Mi

01i

I

H=1 Climi Oaili O-Fili-mi x

g(alt; A ,X)

1

t =(,-, 2,i(l+, j j j

U=11

---

2),-2-rj)

(6.22)

IN)

where

47r(I M) 1 (21 + 1) (1 + m)! -

Cim

=

(-2)111

-

(6.23)

Note that the vector ti satisfies ti-tj -2(-Fi-'F,j)2, particularly ti 2 0. This formula requires only differentiation in contrast to Eq. (6.21), =

6.3

where both differentiation and

integration

Generating

function

needed. To

are

89

couple

the

spherical harmonics to the desired function in Eq. (6.3), one has multiply Eq. (6.21) or (6.22) by q, and sum over x. To construct the correlated Gaussian-type geminals from g we note

solid to

2RBR

exp

=

exp

(6.5)

f

-2

1

iAx

-

2

BR; A + B, x)

---

(x

to

serves

+

-

R)B(x

-

Eq. (6.6).

f

-2 (x

Jc- Ax

-

2

-

R)

+

(x

-

R)j-

generate the function O(x

It is easy to show that

or

exp

9R) g(s

1 -

0('-R)

The factor

-

R)B(x

-

R)

-

(6.24)

R)

of

Eq.

I

IV X

IIIX,_Ri12ki y1irni (X,

-

Ri)

N

02ki+li

fj BkjIj f dtiYjj.j (ti) Oaj 2kj+1j

i=1

x

x

exp

(

-

-1 kBR

-

2

-J-tR)

g(alt + BR; A + B, x)

(6.25)

1

aj.=O,...,CXJV=O ItAr 1=1 it, 1=1-, ...,

or

fn (A, B, R, x) I

I

expf -2 j Ax 2(x -

-

R)B(x

-

R)j

xip i=1

N

3

anip

fj fj atipnip

i=1

x

-

Rip )nip

P=j

exp( 2kBR iR) -

-

P=I

g(t + BR; A + B,

x))

1

(6.26)

6. Variational trial fimetions

90

where

n

stands for the set of

In,,, n12,n13,...,nNj,nN2,nN31-

Tn the

Cartesian representation the parameter a plays no active role but the x,y, and z components of each vector ti, (tillti2lti.), serve to construct the function

O(x

-

R).

To construct the

vector-coupled product OLM(X) of Eq. (6.3), one has to sum over mi's with appropriate Clebsch-Gordan coefficients in Eqs. (6.21) or (6.22). Apparently this is a very tedious task particularly when the number of particles is large. The choice Of OLM(X) of Eq. (6.4) leads us to the following very simple equation which relates the correlated Gaussian to g. By choosAe with a unit vector e, we obtain for t2 tN ing t1 =

V

=

iiX

fKLM (u, A, x)

' =

BKL

f

=_

exp

YL M (' )

(_2I FcAx (

v

2KYLM(v)

d2K+L

g(Aeu; L WA-2_K+

A, x)

dL

(6.27) We

from

Eqs. (6.21), (6.22), and (6.25)-(6.27) that the are explicitly constructed from the generating function g. Depending on the choice of the vector s, g leads to different forms of the correlated Gaussians, when followed by suitable operations acting on s. These are surn-ma J ed in Table 6.2. The construction of fKLM (u, A, x) is simplest among others and it has a wide range of applications as will be shown in later chapters. The correlated Gaussian of Eq. (6.27) contains only the relative coordinates and the center-of-mass motion is dropped from the outset. Thus there is no problem arising from the coupling between the intrinsic motion and the center-of-mass motion. If one uses the singleparticle coordinatesr instead of x in Eq. (6.27), the coupling between them occurs in general and has to be taken caxe of appropriately in can see

correlated Gaussians

order to calculate the energy of the intrinsic motion. A suitable choice of A and u will, however, lead to the result that the center-of-mass motion in

separated from the intrinsic motion. This will be discussed Complement 6.4. Chap. 2 we discussed the linear transformation of the coordi-

can

more

In nates

x

be

detail in

induced

by tJae permutation

P. It is

important

to Imow the

6.3

Generating

function

91

Relationship of the two types of the correlated Gaussians to generating function g of Eq. (6.19). The symbol alt indicates a set of vectors f aiti amtN I. Bkj and Cl,,, are defined in Eqs. (6.9) and (6.23), respectively. Table 6.2.

the

Correlated Gaussians

-I.;v2

exp

Ax) rIN

i=1

(I rIN

1

P01-i f

-

i= 1.

2

i= I

i=1

x

Ylimi(Xi) ali-Mi

ali

I

rIN

jg(alt; A, x))

diiYiini(Z)

-!.,'cAx) IIN

exp

Y1 irni (Xi)

climi aaili ajli-mi

g(alt; A, x)

I

t =(I-, 2,i(l+, j j j

2),-2-rj)

i=O"ri=O (i=l,.. N) .,

ld Ax) IV12Ky f dgYLm( ,) (

exp 1 =

Correlated

Uixi)

i=1

,

x)

).X=O,e=je-j=3-

Gaussian-type geminals

-UMx

-

(In,iv exp

.1 2

2

x

EN

=

d2K+L j,-X2K+L g(Aeu; A,

F3 K-L

exp

(V

J(V)

L IV

2

I

-

,

Bkjjj 2

(x

-

R)B (x

f dii-Yi

RBR

-

I fT7

R)

=,

Ixi _RZ12ki Y1 imi(Xi_ 14)

a2ki+li iM

JiR) g(a It

-

+

BR; A + B, x)

expf .1.7cAx I(x--RR)B(x R) I IIN JJ'=j(Xip =ffrff, lip-=, t-,77ri- jexp(-1:YZBR-!R) g(t+BR; A+B, x))

-j=O,jtjj=j

3

-

-

-

-

, i=-

2

2

3

a7"P

i=

2

p

P

x

ti=o

p

-

Rip )ni,

6. Vahational trial functions

92

effect of P

the correlated Gaussians. Since the correlated Gaus-

on

generated from the generating function, it suffices to examproperty of g due to P. By using the relation Tpx (see Eqs. (2.26) and (2.29)), we obtain a very simple result

sian is

ine the transformation

Px

=

Pg(s; A, x)

=

g(Tp_.9; Tp-ATp, x).

(6.28)

One

only needs to change the matrix A and the vector s appropriately. An important fact is that the generating function preserves its functional form under P. This is also true for a more general linear transformation T of the coordinates x, e.g., a transformation from one set of coordinates to another. Combining this fact with Eq. (6.27), we

obtain

a

very useful

property of the correlated Gaussian fKLM-

Namely for the transformation of Tx

TfKLM(u, A, x)

7--

=

Tx,

we

have

fKLM(TU TAT, x).

(6.29)

Thanks to this nice property one only needs to redefine the parameters A and u of the basis function to construct the transformed wave function. This

property plays

important role

an

in

evaluating

the matrix

elements. The

generating function (6.19) plays a key role in generating the and, moreover, facilitates the evaluation of the

correlated Gaussians matrix elements of

physical operators.

the formulation based

It is therefore desirable that

the

generating function In a many-body system as well. In extending the results to laxger systems of identical paxticles we need to cope with the symmetry adaptation one can use

of the

the

wave

function. Tn such

generating

function

were

a case

on

it would sometimes be useful if

expressed

in

an

"uncorrelated7 form of

the coordinates x, because the symmetry adaptation can then be shnplified by using the technique of Slater determinants or permanents. In fact to the

we can show that the generating function can be related product of the Gaussian wave-packets centered around -4 =

(R,,..., RN) through an integral transformation. Using the definition Eq. (6.51) of Complement 6.1, we can express the product of the

of

Gaussian

wave-packets

as

N

det-V

_'i

ORj (Xi)

)

4

1 exp

:iFx + 2

k_Vx

1 -

2

kFR) (6-30)

with

an

N

x

N

diagonal

matrix

6.3

-YJ

0

0

72

Generating ftmetion

93

0

...

(6.31)

0

'YN

A direct calculation using

1:Mx +

exp

2

2

x)

dx

-9A-18

exp

detA

following equation which relates product of the Gaussians of Eq. (6.30): proves the

2

g of

Eq. (6.19)

(6.32) to the

g(s; A, x)

(detr)3

4

expf 'g(r, Arisl -

-

(47r-) N (det(rT

2

N

g(_V(.V-A)-1s;A(F-A)-'FR)

X

'Y'

ORi (xi)

dR.

(6.33) Note that

A(r

From this

we see

A)-' r

r(r

A)

-1

r

F is

symmetric matrix. The function g in the right-hand side of the above equation depends on the integration variable R and serves as just a weight which is needed to convert the product of the Gaussian wave-packets to the generating function. Equation (6.32) is proved in Exercise 6.2. We have seen that the correlated Gaussians are all generated from the same generating function as summa ized in Table 6.2. Furthermore, the latter can be obtained by the integral transformation of Eq. (6.33) involving the product of single-particle Gaussian wave-packets. -

=

-

that the calculations

-

can

a

be reduced to the matrix

N-particle wave functions involving the product of the wave-packets. The width parameters -yi of the wave packets can be chosen arbitrarily. To choose uniform width parameter for all of them is most convenient if xi indicates the single-particle coordinate of the identical Particles, because then the permutational symmetry of the wave function is simply reduced to that of the "generator coordinates" R. Even when x denotes the set of relative coordinates, this elements of

Gaussian

6. Variational trial fimcdons

94

nice property

be used

by including the center-of-mass coordinate as [311. integral representation of the generating function has been successfully employed in accurate solutions of few-body problems [311 as well as in microscopic descriptions of nuclear systems can

shown in

The

in multicluster models

6.4 The

X.L M

[29, 30].

spin fanction

=

1

cosO -1 .1 (0),

2

Alternatively,

22

.1; 2

-IM) 2

.1 + sin# .1 22 (1),

may set up the

we

.1; 2

.1 2

M).

spin function with

(6.34) a

continuous

parameter such as that of Eq. (6.34) by an elementary method instead of using the successive coupling. Its merit is that the construction of the

spin function is simple, that the evaluation of spin matrix elements

is easy, and

V in

moreover

Eq. (6.34),

that

one can use

continuous parameters such

The construction is done

as

follows. The

Young diagram

spin function with spin S for the N-fermion system

[(N12)

+S

as

in the variational calculation.

(N12)

-

S].

The maximum

weight function

is

for the

[n+ n-I

with M

=

=

S,

XSS, must have n+ spin-up functions and n- spin-down functions. The number of terms distributing n+ spin-up functions among the N

particles terras:

is

NS

=

(,+). Therefore xss is expressed n+

as a sum over

these

6.4 The

spin fimcdon

95

NS

XSS (A)

=

E Ai ii)

(6.35)

-

i=1

characterizing the spin function, satisfy the condition, are not independent 0, where S+ is the spin-raising operator. Acting with S+Xss(A) S+ on XSS (A) yields n+ + 1 spin-up functions and n- 1 spin-down N functions in each term and thus leads to (n++,) independent terms.

ANs)

The coefficients

of. each other but must

=

-

Since the coefficient of each term must N

I

V (n+ 1) (nl+) +

1

=

vanish,

one

(2S + 1)N! + S + 1)! (IN (IN 2 2

has

-

S)!

(6-36)

independent parameters to specify the vector A completely. Here the last minus one of Eq. (6.36) comes from the normalization of the spin function. XSM is easily obtained from Xss(/\) with the use of the spin-lowering operator and thus denoted as XSM(A). The overlap of two spin functions is independent of M and sh-nply given by iV. The independent pa(XSS(A)IXSS(/X')) (Xsm(/\)IXSM(/\')) varied be /X can continuously in the variarameters needed to specify =

=

tional calculation. The ner.

isospin

exactly the same manthe spin and isospin parts in Eq. (6.35), leading to a

function is also constructed in

permutation P on reordering of the terms

The action of the

simply produces

a

linear transformation of the vector /X to another vector denoted

A(P).

96

Complements

Complements 6. 1 Nodeless harmonic-oscillator functions

as a

basis

In variational calculations for bound states it is very important to have a set of basis functions which can approximate square-integrable

functions to any desired accuracy. For a single-variable function one may use the well-known complete, orthonormal eigenfunctions of, e.g., the harmonic-oscillator

(HO)

Hamiltonian. Or

one may try to use functions which may not be complete mathematically able to cope with many problems flexibly and, from a practical

nonorthogonal but

are

point of view, accurately. The amine the

possibility

functions. We will

by studying

purpose of this

of nodeless HO functions the

see

performance

Complement

is to

ex-

set of such "basis"

as a

of the nodeless HO functions

how well

they approximate a given function f (r). The nodeless HO functions with angular momentum Im have

continuous

parameter

-Palm (T)

=

Nal

( V3)

14 I/r

exp

2

T

with

a

solid spherical harmonic

the normalization constant

(2 1+2 a"

a

a:

2)y7n(,VF

(6.37)

I/r

1

(see the following Complement). where

Nj

is

given by

2

2

Nal

Here

(6-38)

=

(21 + 1)!! is introduced to scale the

length. The Gaussians employed in Complement 8.1 to solve the ground state of the hydrogen atom are 0. The overlap of two nodeless HO functions is special cases with I simply given by v

=

(-Vaiml-Va-'im)

aa1

Na I IVa'I

2

2

(6.39)

_

=

.

+.,1)2

(a+a)2 2

2

We attempt to approximate a normalized function momentum ITn in terms of combinations of

fl,,, (r)

with

angular

K

Am (T) The ance

error

cirailm (T) of the

approximation

(6.40) is estimated

by calculating

the vaxl-

C6.1 Nodeless harmonic-oscillator functions

0-

2(f)

=

fI

cillil,,-,

,,

97

a

set of

Or)Idr.

parameters

(P.41)

jal, a2,..., aKI by

the trial and

may set them up

by SVM. Once they are selected, minimizing 0-2 to determine the ci's priate way

basis

2

fl (r)

One may choose or

as a

error

leads to

some

appro-

procedure a

linear

of the

equation

K

E(Failml-Vajim)cj =' (Faiiralfim)

(i

=

1,

...,

(6.42)

K),

j=1

andthena 2 is As

a

I

given by

test function

K

-Y:ij=iCi*Cj(-Vai1mIrajIm)-

fim(r)

we

first take up the HO

wave

functions

angular frequency w hy/m, where n is the number *,,Im (r) of radial nodes. We employ a phase convention such that the radial HO wave functions are all positive for r greater than the outermost nodal is needed to point. The overlap of the functions Fal (r) and calculate o-2. It can be obtained by using a generating function of the with the

=

..

HO functions

Ik

4

A(k,,r)

exp

2

+

Nf2-vk-r

2

1 VT

-

2

21 (6.43)

0,,jm(r)*P,,jm(k), n1m

polynomial of the complex Bargmann space variable k, is the Bargmann transform [76, 771 of the HO wave functions in a spherical basis and its explicit form is given in terms of the solid spherical harmonics of (4.5) [781

where

Pnjm(k),

a

:(2

P,,lm(k) where

Bn1 n -

1) n + 1)! (2n

(6-44)

(k k) ny1m (k), -

Bnj, defined in Eq. (6.9), is the coefficient needed to Legendre polynomials Pl(x):

express xm

in terms of the

xm

21+1

E

=

4r

(6.45)

BnIP1(

2n+l=m

Expanding

(6.44),

we

the

overlap (F ,lm (r) I A(k, r))

obtain

in terms of the

polynomials

Complements

98

(-PaimlOnlm) Obviously,

(2n + 21 + 1)!! (2n)!! (21 + 1)11.1

the

1

(1+ )n (

2n)+!!

-

approximation

in

-

a

Eq. (6.40)

2

2Va

a

1 +

(6.46)

a

becomes less trivial

the number of radial nodes of

as

1 f increases. For Onlm (r) wit"h n 2, the combination of merely a few (::5: 3) terms leads to very good 5 it is hard to make u 2 less than approximations, whereas for n 10-10 with a double precision calculation. This is so because all ai's tend to take a value of unity, reflecting the fact that such a HO function can be expressed by combinations of higher order derivatives of Falm(r) with respect to a at a 1, and the optimization procedure tends to construct such derivatives out of -Tal,,, of almost equal parameters. One thus has to deal with an almost singular overlap matrix ((Faiiml-Vajim)) to obtain the solution of ci's. In stead of approximating each of the 0,,,. (r) with different sets of =

or

=

=

1),

(j:IV n=O 0r2(0nIM))/(N-.L

minimized the average value, (U2 )N with a single set of ai's. The values of the

ai's,

we

follow

a

=

geometric progression and

cessive terms

were

determined

of ten nodeless HO functions The next test

example

k

ai's

were

assumed 11-o

its first term and the ratio of

by Powell's method [141.

yielded (a 2)8

=

0.6

x

suc-

A combination

10-10 for I

is the shifted Gaussian defined

=

0.

by

I

( 3)4 (_IV(,r2+S2))jI(I/'Sr)y V

(r)

=

Fj

exp

-

where the function

ii(x)

(6.47)

7 IM

2

7F

is the modified

spherical

Bessel function of

the first kind

ij(X)

=

F '7-x'I,+.! (X) 2

X2k+1

1: (2k)!! (2k + 21 + 1)!!'

(6.48)

k=O

and where the normalization constant Fj is 4e

2

'us

with

F,j

2

(6.49)

2

To get the normalization constant, 00

fo

x

e-ax21, (bx) 1, (ex) dx

which is valid for Rea

>

Gaussian

wave-packet

I =

2a

0, Rev

shifted Gaussian because it is

we

>

have used the formula 2

exp(b +c2),,'(bc)'

-

4a

1. The function

closely

centered around

2a

(6.47)

related to the s

(6.50) is named

single-particle

C6.1 Nodeless harmonic-oscillator functions 3

,ps' (r)

99

(6.51)

11

-

2

T

through

basis

1 exp,

-

as a

the relation

4V'7-r Os

(6.52)

1M

Fj 1ra

Here

use

eVr_5

is made of the

=

evrscos'o

=

equation

E(21 + 1)ij(vrs)Pj(cosO)

(6.53)

1

with the rem

angleO between r and spherical harmonics

s, and the well-known addition theo-

for the

I

4w-

Pi (CosO)

1:

=

21+1

yjm(i )Yjm( )*

ra=-l

=

4-x-(-I)' /2_71-+I

lyl(p)

X

(6.54)

YIM100.

8 The radial paxt of the shifted Gaussian is hence peaked at r shifted the be to therefore would It approximate challenging -

/_2, Iv.

Note that large s in terms of the combinations of A e-211 A of of in terms as Eq. (6.43) expressible (NF2'91 T). 0,v(r) The overlap between the functions F,,la(r) and 7p,jn(r) is

Gaussian with

1

2

is

(r,im 1,0SW

v/-2-

N,, 1 Fs

1(1 + a)'+' 2

P(_ 1+a

ex

V I/

(6.55)

Assuming again that the ai's follow a geometric progression, 0-2 was minimized by Powell's method for a given value of ;. For the case 2 0 it is possible to make o- < 10`0 with ten nodeless HO of I =

functions for the shifted Gaussians of up to :! 10. All ai then tend to take values close to each other for large,;, and this requires a very

equation (6.42). Increasing the number 2 of nodeless HO functions gives us even smaller o- values and widens precise solution of the

the range of maximum approximated well.

linear

(;

value in which the shifted Gaussian

can

be

examples strongly suggest that the nodeless HO functions can approximate square-integrable functions to any desired accuracy, though the number of nodeless HO functions needed depends The above

Complements

100

on

the

shape of the

test function. A remarkable

shows that the linear function

approximated to high

r

itself, defined in

accuracy in terms of a

in

example given

[66]

finite range, can be combination of Gaussians a

e-ar2 ) We stress two remarkable points of the nodeless HO functions. One a combination of a few nodeless HO functions can approximate

is that

the shifted Gaussian is easy to make

2 a

even

with

less than

nodeless HO functions. In

an

a

large

value of

10-1-0 with expansion

a

;.

For

example, it only 15 HO functions,

combination of

in terms of

would need many more terms to obtain the same accuracy. This indicates the flexibility of a nonorthogonal Gaussian "basis" compared one

to the

orthogonal basis such as the HO functions. Another point is that there are many, possibly an infinite number, of sets f a,,..., aKI which approximate a given function equally well, even though the number K is fixed. This is what we have experienced in the above examples. We display graphic illustrations of Gaussian expansions for different functions with I 0. The most appropriate nonlinear 0, m paxameters ai are determined by optimization, while the linear ones ci are given by the solution of the least square equation (6.42). To point out the dependence on the number of Gaussians, we use different numbers of terms in the expansion (K 5, 10 and 20). In the first example we approximate the HO function 05oo(r) by =

=

=

Gaussians. This function is smooth but oscillates and

asymptotically falls

off like

a

(it

has five

nodes)

Gaussian function. As shown in

10 and K 20 Gaussians give a perfect fit to the 6.1, K function, so these curves are practically indistinguishable. =

In

=

the second

to fit

Fig.

exact

an exponential function e-', the wave function of the ground state of the hydrogen atom. The asymptotics of this function is quite different from that of a Gaussian. To approximate the asymptotic part of this function one needs many terms of Gaussians as is illustrated in Fig. 6.2. By increasing the number of Gaussians one has better and better agreement in the asymptotics. After a certain distance, the Gaussians fall off much more rapidly than the exponential function. In many practical applications, especially for bound states, however, one can always use enough Gaussians to reach the required accuracy. We note that the Gaussian fit gives a poor value (zero) for the derivative at the origin (the exact value is -1) as will be discussed in Complement 8.1. In the next example we try to approximate the absolute value fimction f (r) 12.5-rl. The Gaussian expansion, again, does a pretty

f (r)

=

=

case

we

attempt

C6.1 Nodeless harmonic-osefflator functions

as a

basis

101

10

5

0

-5

-10 0

4

2

6

8

r

0, m 5, 1 0) and its Fig. 6.1. The harmonic-oscillator function (n approximations by Gaussian expansions. The solid curve is the (UM3.ormalized) harmonic-oscillator function f (r) V 500, and the dotted, dashed and 5-, 10- and 20-term Gaussian expansions. long-dashed curves are the K The 10- and 20-term. expansions are practically indistinguishable from the -

=

exact

curve.

100

IT

-C

20

10-40

--60

10

40

10

0

10

30

20

40

50

r

Fig. 6.2. The exponential function and its approximations by'Gaussian exp(-r), expansions. The solid curve is the exponential function f (r) and the dotted, dashed and long-dashed curves are the K 5-, 10- and 20-term Gaussian expansions. =

=

102

Complements

good job (Fig. 6.3), would expect

of further Gaussians

by the inclusion

and

an even

one

better fit.

3

2

V

1

0

0

1

2

I

I

.

3

4

5

r

Fig. 6.3. The absolute value function and its approximations by Gaussian expansions. The solid line is the absolute value function f (r) 12.5 -,rl, and the dotted, dashed and long-dashed curves are the K 5-, 10- and 20-term Gaussian expansions. =

=

The approximation for the step function, f (r) 1 if 7- < 2.5, 2 if r > 2.5, is less impressive (Fig. 6.4), but it goes without f (r) that it is not trivial to fit that function. One can improve the saying =

=

fit

by increasing

the number of

Gaussians,

be pretty slow. The last example shows that

adequate

in

some cases.

Let

us

with Gaussians. This function is it simulates the behavior of

a

try

but the convergence

might

Gaussian expansion may be into

approximate f (,r)

practically

a wave

zero near

function of

a

the

12 =

r

2

e-T

origin, and

system -with very

core. The Lenard-Jones or other hard-core potentials such a function. Figure 6.5 shows that the Gaussians produce may generally give a good fit to this function. By scrutinizing the inner

strong repulsive

part of the approximation

reality

(see Fig. 6.6)

the Gaussians do not

produce

one can

exact

see,

however, that

zero near

the

in

origin, but

C6.1 Nodeless harmonic-oscillator functions

as a

basis

103

3

2

C, -

0 0

Fig.

6.4. The

1

2

3

4

5

step function and its approximations by Gaussian expansions.

The solid line is the step function f (r) = I if r < 2.5, f (r) and the dotted, dashed and long-dashed curves are the K 20-term. Gaussian

2 if

r > 2.5, 5-, 10- and

expansions.

the

approximate function oscillates around the exact one even for 20 Gaussians. This oscillation may be very unpleasent: To tame the hard core potential, we need a wave function which is effectively zero near the origin. The oscillating function leads to numerical problems, which makes it rather difficult to obtain the solution of interaction has

a

very

It is

problems

where the

strong hard-core part.

to know the

important completeness of the basis functions in L (square integrable functions), H1 and H2 (first and second Sobolev) spaces because the bound state in quantum mechanics is traditionally 2

formulated in L 2, and the mathematical solution of the

equation is formulated in H' and H2

spaces.

(The

Schr8dinger

space HI is

a

set of

functions whose derivatives of up to the mth order are all square integrable. Note that the kinetic energy operator requires the second order derivative of

a

basis

variational method

ple

in

[791,

and the

function.) are

The convergence properties of the Ritz demonstrated in H1 and H2 spaces, for exam-

completeness

in L 2 is not sufficient to

guarantee

the convergence of the Ritz method. The proof of the completeness in the space of L 2 and in the spaces of H' and H2 is presented in

[801.

This work proves that any function

can

be

approximated

to any

Complements

104

200

150

100

50

0

-50

-j

-100 0

1

2

3

4

5

r

Fig.

expansions. dashed

The solid

curves are

10 and 20 term

curve

the K

=,r

and its

is the ftmction and the

=

expansions

12e_,r2

approximations by Gaussian dotted, dashed and long5-, 10- and 20-term Gaussian expansions. The

f (r)

6.5. The fimction

are

practically indistinguishable from

the exact

curve.

0.002

.

.

.

.

.

i

.

.

I

I

0.001

0.000

-0.001

-0.002 0.0

0.1

0.2

0.4

0.3

0.5

0.6

r

in Fig. 6.5, but the inner paxt is 5- and 10-term Gaussian expan i n scope and not drawn here.

Fig.

6.6. The

curves

same as

with the K

=

magnified. axe

The

out of the

C6.2 Solid

prescribed

accuracy with

spherical

linear combination of

a

that the number of Gaussians in the the parameters of the Gaussians

harmonics

105

Gaussians, provided

expansion is sufficiently large and

are

appropriately

chosen.

6.2 Solid

spherical harmonics The solid spherical harmonic Yl,(r) r1YI,(i6) of Eq. (4.5) is a 0. 0, of the Laplace equation, V2f (,r) solution, regulax at r The irregulax solution is given by r-1-'YI (f). The solid spherical harmonic is a homogeneous polynomial of degree I in the Caxtesian =

=

==

..

coordinate:

21+1 +

rlyl.(,P)

(1 + Tn)! (I

47r

-

m)!

p! q!

p

-

q)!

pq

(_X+i )p (X _iy)q Y

X

2

where p and q p + q <

1,

p

-

=

(6.56)

7

positive integers which satisfy the conditions The complex conjugation leads to Yl,,(,P)*

are

q

ZI-p-q

2

m.

(-I)MY1-09It is easy to show that with 7-21i(l + 7-2) -2-r) we obtain

(t-T)i

=

(X

+

iY

2 -

-F

(X

_

iY)

I

M)! where C1. is it

(

given

in

vector t

(I

-

2TZ)I

-F'-'YI,,, (r),

C1

=

(6.57)

Eq. (6-23).

the condition 0 < 1

-

m

<

al

aal This

_

special complex

For a given 1 the power of -F must 21, which guarantees the range of m should. Equation (6.57) leads to the equality

satisfy as

a

eat-r

=

CIMYIM(r)-

(6-58)

a=O

simple relation was used

in Sect. 6.3 to

generate the angular part

of variational trial ftmctions. 2

By expressing the Laplacian as V2 the solutions of the

I =

a

T2- Yr-

a (r 2 -a-,

we see

that

equation

[V2_(n-1)(n+1+1) I f(r)=0 r2

(6-59)

Complements

106

expressed

be

can

When

n

1

=

in

or n

polar coordinates as r'Y,,,,(r) or -1 1, the equation reduces to

=

-

the

Laplace

equation. The inverse relation of

Eq. (6.56)

where 1 takes the values n,

given

it is

as

follows:

n

-

2,

...,

0

or

(6.60)

npq 1. A hint to calculate BIM

in Exercise 6.3.

jjIM1j2TtI2j3Ta3)

IT

expressed

BPq Yl,,, (i6),

XPY qZn-p-q =,rn

is

is

(6.61)

j

=

U1 +j2) +j3

=

il

U2 +j3)

+

possible

J12 +j3

to choose

ii

a

+

(6.62)

J231

basis in which

j212, j2, J, j2, 2 j2, 3 1 j2,

are

diagg-

onal

(6.63)

ljlj2 (J12) h; jM) 7

or a

basis in which

2 j2, 1 j2, 2 j2, 3 123, J2i Jz

jil j2h (J23); JM) i

expressed

in terms of

ljlj2 (J12), h; JIVI)

diagonal

(6.64)

-

The transformation from the it is

axe

=

a

one

basis to the other is unitary and

U-coefficient

as

E U(jlj2 Jh; J12 J23) jil, j2h (J23); JM) J23

C6.3

Angular

momentum

recoupling

107

(6-65) The U-coefficient is often called

by

the

overlap

U(jlj2 Jh; J12 J23) and is in fact

a

unitary Racah coefficient.

It is

given

of the two basis states

(il j2h (J23); JM ljlj2 V12) h; JM) (6-66)

:::::

independent

1

i

i

of the

magnetic quantum number

M.

By using Clebsch-Gordan coefficients, the unitary Racah coefficient can be expressed as

(jITn1j2?n2jjI2MI2

U(jlj2 Jh; J12 J23) MIM2M3MI2M23 X

(JI.2Ml2j3M31JM)(j2M2j3M3lJ23M23)UIMIJ23M231jm)(6-67)

Note that in the above

equation M

is fixed to

certain value in the

a

range of -J < M < J, so that actually only two m values are independent in the summa i n. As the Racah coefficient is real and

unitary, the (U-1 Ut =

inverse transformation of

Eq. (6.65)

is

simply given by

CT)

=

U(j1j2 Jh; J12 43) ljlj2 (42) h; JM)

jil j2h (J23); JM)

1

7

J12

(6-68) If the basis of the it is

Eq. (6.63)

is to be transformed to

and

angular momenta j, coupled with i 2 to

transformation coefficient is

ljlj2 (42) h; JM) 1

=

=

j3

axe

the total

first

angular given by

coupled

a

to

basis in which

J13 and then J, then the

momentum

(-l)jl+j2-J12 ji2il (J12)

(-l)jl+j2-J12 1: U(j2jI Jh; J12 J13) jj2

i

i

h; JM)

j1h (J13); JM)

J13

=

E(-J)jl+J-J12-JI3 U (j2jl Jh; J12 J13) ljlj3 (J1-3)

7

j2; JM)

J13

(6-69) unitary Racah coefficients are transformation coefficients becomplete sets of states, so that they obey orthonormality and

The tween

Complements

108

completeness relations. The orthonormality condition (jl,j2j3(J231); JMjjI j2h (J23); JM) Jj ,3 j,,,,, reads, with the use of Eq. (6.68), as 7

E U(jlj2 Jh; J12 J23) U(jlj2 Jh; J12 J231)

:_

(6-70)

JJ23 J23'-

J12.

The

relation may be

completeness

E (jlj3 (J13)

7

expressed

as

j2; JM ljlj2 (J12) h; JM) i

J12

(jlj2 V12) h; JIVII-ljlij2j3(j23); JM)

X

7

-

i

i

in terms of the Racah coefficients to

equation can be transcribed following relation

This the

(6.71)

Ulh V13) j2; JMIj1 j2h (J23); JM)

E (-I)jl +J-J12 -JI3 U(j2jI jj3; J12J13) U(jlj2Jj3; J12J23) J12

(-1)32+j3-J23 U(jlj3Jj2; J13J23)There

are

symmetry relations with respect

among the six seen

curly

(6.72) to the

interchange

momentum labels. These relations

angular by introducing the

so-called

6j symbol [70, 72, 751

can

be best

written

by

brackets

U(jlj2Jj3;j]-2J23)=(-I)jl +j2 +j+j3 Af(2JI2+1)(2J23+1) X

1

il h

j2 J

because the symmetry relation of the one can show that

U(jlj2Jj3; J12J23)

=

(-l)j2+J-JI2-J23

=

is rather

+ 1)(2J, J1 223+1)

(2j2

+

simple. E.g.,

U(Jj3jlj2; J12J23)

U(jlJj2j3; J2342)

=

rL2

U(Jl2jlj3 J23; j2 J)

(6.73)

6j symbol

U(j2jlj3J; J12J23)

U(j3Jj2jl; J12J23)

X

J12 J23

1) (2J + 1)

C6.3

If

one

U(j2 J12 J23 J; j1h)

of the

(6.74)

-

efficient has the value +1. If J12 =

=

109

recoupfing

2

labels, ji, j2, j3,

U(jlj2jlj2; J120)

momentuin

(2JI2,+ J,2+ 1)(2J23 + 1) + 1) (2j3 + 1) (2j, +

(_l)jl+j3-J12-J23 X

Angular

or or

J, is zero, the unitary Racah J23 is zero, then we have

co-

U(jljlj2j2; OJ12)

(-l)ll+j2-J12

p2

2J12 +1

+ 1) (2j2 2j,+ (2j,

The above discussion is extended to the

case

+

(6.75)

1)

involving

four

com-

muting angular momentum operators, jlj2,j3,j4. A basis with a good total angular momentum J and its z component J, is constructed as, for example,

jj1j2(JI2)J3j4(J34);JM)

or

ljlj3(J13)ij2j4(J24);JM)- (6-76)

The transformation ftom. the basis in which J12 and

quantum numbers numbers is

to the basis in which

J13 and J24

are

J34 are good good quantum

again real and unitary:

ljlj2 (J12) j3j4 (J34); JM) i

J13 J24

31

32

h J13

j4 J24

J12 J34

ljlj3 (43) j2j4 (J24); JM) 1

-

J

(6-77) The transformation coefficient is

recoupling coefficient between four angular momenta called a 9j symbol in unitary form. It is independent of M and given by (jIj3(JI3)J2j4(j24); JMjjIj2(j12)J3j4(J34); JM)i a

that is

il h J13

j2 j4 J24

J12 J3 4 J

M I M 2 M3 M4

IVI 2 M3 4 MI 3 M2 4

(jlMlj2M2ljl2MI2)(j3M3j4M4lJ34M34)(Jl2Ml2J34M341JM) (il7nlj3Tn3lJl3Ml3)(j2M2j4M4lJ24M24)(Jl3Ml3J24M241JM)(6-78)

Complements

110

again that M is fixed to a certain value in the range of -J < M < J, so that only three m values axe independent iTi the above summation. The inverse transformation is given by

Note

ljlj3 (J13) j2j4(J24); JM) i

A

j2

h

j4

J12 J34

J24

J

J13

J12J34

ljlj2 V12) j3j4 (44); JM) i

(6-79) The

orthonormality and completeness relations for the unitary 9j

coefficients

can

il h J13

J13 J24

be derived

as

before:

J12 J34

j2 j4 J24

il h J13

j2 j4 J2 4

A

J2

h J13

j4 J24

J12 J3 4

J

(-l)j3+j4-J34 J12J34

L

j3-j4-J23+J24

There

are

many

il j3 J13

JJ12JI2"JJ34JS4"*

J

J

J

A

j3

j4 J14

j2 J23

L

il j4 J14

j2 h J2 3

J1-2 J3 4 J

J13 J2 4

j

(6.80)

J

symmetry properties of the unitaxy 9j coefficient.

These will have their

[70, 72, 751

J121 J341

simplest form in curly bracket

terms of the familiaz

9j symbol

written in

j2 j4 J24

J12 A4

-\/(2JI2+1)(2J34+1)(2Jl3+1)(2J24+1)

J

X

1

il h J13

j2 j4 J24

J12 J3 4

Using the symmetry properties of the 9j symbol, il h

j2 j4

J12 A4

j2

j4

J13 J24

J13

J24

J

J12

J34

J

J3

(6-81)

J we

have for

example

C6.3

Angular

momentuin

j + 1) (2J34 + 1) (243 + 1) (2J12 (231 + 1) (2h + 1) (2J + 1) (2jj -

-

(243 + 1) (2J24 + 1) (2J34 + 1) =V, 3

(2j3 (233(2. 3.3 + 1) (2j4 + 1) (2J + 1)

(-l)jl+j2+j3+j4+JI2+J34+JI3+J24+J

Ill

recoupling

j2 j4 J24

J12 J3 4 J

j3 J13

J13 il j3

J24

i

j2 j4

J12 J34

33

34

il J13

j2 J24

31

J34 J12 J

(6.82) For

One may consider other basis states than those given in Eq. (6.76). example, the basis in which J12 and J34 are diagonal can be trans-

formed to

pled

as

basis in which the

a

angular

momentum is

successively cou-

follows:

ljlj2 (42) j3j4 (J34); JM) 7

E U(J12j3 Jj4; J123 J34) jj1j2 (J12)

7

j3 (J123) j4; JM) 7

-

J1,23

(6-83) The

9j coefficient

rewrite the state in

coupling,

as

be

expressed in terms of products of unitary Eqs. (6.69) and (6.68) enables one to Eq. (6.83), which is obtained by the successive can

Racah coefficients. The

use

of

follows:

jj1j2 (J12) h (J123); j4; JM) i

(-J)jl+J123-JI2-JI3 U(j2jlJl23j3; J12J13) J13 X

jj1j3 (43), j2 (J123), j4; JM

(-j)j1+J123-J12-J13 U(j2jlJl23j3; J12J13) J13 J24 X

U(J13j2 Jj4; J123 J24) jj1j3 (43), j2j4 (J24); JM) (6.84)

Complements

112

Substituting this result leads to

useful

a

il h J13

j2 j4 J24

into

Eq. (6.83) and comparing with Eq. (6.77)

identity J12 J34 J

E(_j)jI+JI23-JI2-JI3 U(Jl2j3Jj4; J123J34) J123

U(j2jljl23j3; J12JI3) U(Jl3j2Jj4; J123J24)-

X

(6.85)

application of the above equation, we note that if one of angular momenta is zero the 9j coefficient is expressible i-n terms of Racah coefficients. E.g., we have As

an

nine

ilh J13

0

31

j4 j4

A4

U(jlj3Jj4; J13J34)i

J 0

h J13 0

h h

6.4

j4 J24 j2 j4 J24

:

6

J

2 243 + 1

2j, (2j,

J

+

1) (2j3

+

1)

U(J13jI Jj4; h J24)

i

32

(-l)j4+J-J24-J34 U(j2j4Jj3; J24J34)- (6-86)

J34 J

Separation of the center-of-mass

motion from correlated Gaussians

The correlated Gaussian

(6.27) in the global vector representation is, among the several possibilities of the correlated Gaussians, most easily constructed from the generating function. Thanks to this simit has

wide range of applications. The relative coordinate (xi, ___j xiv-1) is used to represent the correlated Gaussian, so that the center-of-mass motion is dropped from the beginning. The

plicity ;

a

=

aim of this

Gaussian is

Complement is to expressed in terms

fKLM (u, A, r)

=

exp,

show

that, even when the correlated of the single-particle coordinates r as

(_2'fAr) V2Ky M(V) L

C6.4 Separation of the center-of-mass motion

113

N V

(6-87)

wri,

possible to separate the intrinsic motion, expressed in terms of the relative coordinates, from the center-of-mass motion by requiring some special conditions on the parameters A and u. Here A is an N x N symmetric matrix and u is an N x I one-column matrix. Therefore, in it is

the correlated Gaussian basis the

always absolutely necessary used

use

of the relative coordinates is not

but the

single-particle coordinates can be following. correlated Gaussian of Eq. (6.87) can be

well. We shall show the conditions in the

as

By using Eq. (2.4), the expressed by the relative coordinates x and the center-of-mass dinate xN, which are again denoted as x:

fKLM (Ui Ai 7)

=

fKLM (U A! X) i

coor-

(6.88)

7

with

A'

=

U---IAU-'

The matrix elements

U,

and

A!Nj

=

=

A!jN (i

U--IU. 1, give

=

...'

and center-of-mass coordinates and

(6.89) N

-

1)

rise to

pendence of the function. The element A!Nlv

is

a

connect the relative a

center-of-mass de-

parameter describing

the center-of-mass motion which has Gaussian form. Thus the separation between the intrinsic motion and the center-of-mass motion is made

possible by requiring that

XNi where

c

=

is

0

an

(i

=

I,-, N

1)

and

XNjV

=

c,

arbitrary positive constant. As (U-I)iN=l (i

the above conditions N

-

are

rewritten

as

=

11.... N),

follows:

N

I:I:Ajk(U-I)ki=O

and

j=1 k=1 N

N

E 1: Aik

=

(6-90)

C-

j=1 k=1

The center-of-mass contamination in the

YLm(v)

can

be removed

by requiring that u1V

angular function V2K =

0, that is,

IV

Euj i=1

=

0.

(6.91)

Complements

114

and

(6.90)

The conditions

(6.91)

ensure

that the correlated Gaus-

is free from any contaminations due to the center-ofmotion. The intrinsic motion is described by the correlated

(6.87)

sian mass

Gaussian of type (6.27) and the center-of-mass motion is given by exp(-cx'N /2). The number of parameters contained in the function

N(N + 1)/2 + N, whereas since there axe (N + 1) condi(N 1)(N + 2)/2 free parameters. This number is of course equal to the one which the correlated Gaussian (6.27) has: (N 1)!V/2 + (N 1) (N 1) (N + 2)/2. It is instructive to see how Eq. (6.90) leads to the separation of the (6.87)

tions

is

we

have

-

=

-

-

-

center-of-mass motion. For this purpose part of Eq. (6.87) can be rewritten as

note that the

exponential

1

I

(- 2 FAr)

exp

we

exp

a

-2

j(,r, _,rj)2

2

(6.92) where aij

and,3i

are

related to the matrix A

by

N

aij

-Aij (i 7 j),

=

gi

=

1: Aki-

(6-93)

k=1

The

coupling

between the intrinsic motion and the center-of-mass

tion arises from the second term in the exponent. As ri is

mo-

expressed

as

IV-1

7'i

E (U-l)ijXj + XN7

(6.94)

j=1 we

have N-I

N

X2N

Ep,r? i

i=1

N

(

Pi(U-l)ij

+2 j=1

xj

*

xN +

i=1

(6-95) Here the symbol

...

denotes the terms that

coordinates and have

quadratic in the relative xN. Substituting 3i of Eq. are

dependence (6.93) and using the condition (6.90), we obtain that 0. EN EN j= 1_ Aki(U-l)ij k= I EN j= 1)3i ((,T-l)ij =

no

on

=

EiN=1,3i

=

c

and

C6.5 Three electrons with S

6.5 Three electrons with S Let

M

construct the

us

=

1/2

11)

1/2

115

1/2

=

function with S

spin

=

=

The basic terms for

1/2.

are

I ITI),

=

12)

=

13)

1111),

=

(6.96)

I ITT),

assumed to be in increasing

order, e.g. in the state 11) the first and second electrons are in a spin-up state while the third electron is in a spin-down state. The requirement that S+X(A) must vanish leads to the condition Of /XI + -X2 + A3 0. By taking account of the normalization the spin function can be parametrized by a single variable &(-,xl2 < 6 < 7r/2) as follows:

particle indices

where the

are

=

1

(V/jcos,0 VilsinO) I TIT) ( F, coso 4 sin i ) I IT). 2

X.L

i 22

sinO

(A)

+

-

The,O value is chosen such that,&

=

with the intermediate Spin S12

0 whereas V

S12

(6.97)

I

+

=

0

corresponds =

to the

7r/2

spin function

to the

one

with

I-

=

By acting with S-

on

Eq. (6.97),

we

obtain

2

X.1

_.L

2

2

(A)

=

+

These

baryon

:3sin,& 1111) (61 41sin,&) (Vj cos,0 4 sin,&) 1111). -

_

-

+

spin functions

wave

c Os'&

can

functions. See

6.6 Four electrons in

be used for the

Chap.

spin part of three-quaxk

9.

arbitrary spin arrangement Complement 6.5 gives us the following of the four-electron system. For function general spin an

Arithmetic similar to that of result for the S

=

0:

Xoo (A)

(2

(6.98)

in,&

+

COO + 2

sinO)

(2Icos,&

I -

inO)

cosO + 2

ril-isind)

Complements

116

I

+

(2

COO

-

FWIi.6)I lilt) F3 sinO I JITT),

(6-99)

+

where the paxameter 6 satisfies -T/2 < V < -Ft/2 and is chosen such that,O 0 corresponds to the spin function with S12 07 S123 1/2; =

=

=

1i S123 corresponds to the one with S12 and two of electrons molecule two consisting positronium 1/2. positrons, the most important spin function is such that the spins of 0. the identical paxticles are coupled to zero, which corresponds toO

whereas V

=

-r,/2

=

=

In the

See Sect. 8.3. For S

=

1:

ezzsindsin o

X11 (A)

2 +

3

F1!is 4's 4S

sin,& cos o

( ilc -(61

+

osv

-

cos'O +

-

in,&

sin o)

in,& cos p

-

r!2is r!is

in ? sin

p)

in 6 sin

W)

1

inO cos W +

7

(6-100) where the parameters V and W satisfy --F,/2 < 0 < -F,/2 and W < 7r/2. The three independent spin functions with definite

-Ti-/2

<

S12 and 0 S123 values correspond to the V and (p values as follows: for S12 and S123 O for I and 6 and S12 S123 0; 1/2, 1/2, T-/2 I and for and 6 and S12 S123 0; 3/2, z/2 Ti-/2. W o =

=

=

=

=

=

6.7 Six electrons with S

=

=

0

spin functions may be constructed from those of a smaller group of electrons through angular momentum couplings. As an example, let The

spin function of the six-electron system with S 0, Xoo (A), from two groups of three electrons. Clearly X00 (A) is given as us

a

construct the

=

combination of two terms with xoo (A)

As two

tion

=

122 00)

cosO .1 .1;

S123(= S456)

+ sin V

=

1/2

or

3/2:

1!!; 00).

already mentioned, the spin function with S123 0 or 1, and similaxly independent states with SI-2 with S456 has two independent states with S45 1/2 was

=

=

(6.101)

22

=

1/2

has

the fimc=

0

or

1.

C6.7 Six electrons with S

Therefore the first term of the

parametrized I I

00)

as

=

right-hand

side of

=

0

Eq. (6.101)

117

can

be

follows:

COS

sin 61

611 (S12

COS

62

=

1 (S12

0)"17 (S45 2 =

00 0) '1; 2

=

0) 2 (S45

sinVI sin V2 COS

V31 (S12

sin 01 sin #2 sin

631 (S12

=

=

=

00 1) '1; 2

1) 2 (S45 1) "2 (S45

=

=

I

00 0) *'; 2

1) '1; 2

00)

(6-102)

hand, the spin function with S123 3/2 or S456 3/2 has just one independent state and needs no angle parameters. Each term of the above equation and the second term of the right-hand side of Eq. (6.101) can be easily written down in the form (6.35), e.g., On the other

(S12

=

=

=

0) 211 (S45 I -

2v,f2-

00 0) '1; 2

=

(I

-1 ITIJIT)

+

+

(6.103)

+

The four parameters of the five

6, #1-, 02,,03 determine the relative weight independent spin states for the six-electron system with

S=0It is of

course

possible

to start with other

groups of four electrons and two electrons trons.

or

groupings such

as

two

three groups of two elec-

Exercises

118

Exercises Eq. (6.7).

6.1. Prove

Solution. Let

IT

Of

= -

f

course

us

consider the

V)2K+Ldb

YLm (&) (a

I is

equal

E

=

With

U

=

2 1 + -C2-

BKLa 2K+L V2KyLM(V) from Eq.

to

calculate I in another way,

(a.V)2K+L

quantity

(6-104) (6.18).

To

the relation

we use

(2K+L)! p!q!

(a-xj)P(a-X2)q.

(6.105)

p+q=2K+L

[YI, (a)

x

x

Y1, (xl)loo [Yi, (a) 11 12

0

A

A

0

x

Y1,,(a)],\ x1YI1 (XI-)

2A+I

(211+1)(212 X

IYX(a)

X

Y12 (X2)] 00

0

11 12

[[YI, (a)

X

X

Y12 (X2)]AIOO

+,)a11+12C(l, 12; A)

1Y1J-(XI)

X

Y12(X2)1,\100-

(6.106)

coupled form [Y,,_ (a) X Y12(a)],x, is reduced to a 11+12C(II 12; A) Y by using Eqs. (6.10) and (6.11). When using Eq. (6.106) in Eq. (6.104) and integrating over b., we see that A is restricted to L, because otherwise the integral vanishes due to the orthogonality of the spherical harmonics. We thus obtain The

f YLM01)[YA(a)

X

1YII(XI)

X

Y12(X2)],X]00d&

119

Exercises

[YI XI)

JAL

X

Y12 (X2)1 LM

(6-107)

-

Combining these results leads to Eq. (6-7). 0. Then p + q is Consider Eq. (6.105) for the special case of K equal to L. Since 11 and 12 have to satisfy the condition L < 11 + 12 ":: L. Equation (6.7) then simplifies p + q, 11 + 12 must also be equal to =

to the well-known formula

YLM(XI

X2)

+

=

JX1

+ X2

I'F'YLM( XI +X 2)

L

EDOL

=

010 L-I

1XI (Xl)

YL-1 (X2)] LM

X

1=0 L

1+41')

4-) 47r(2L + 1)! [Yl(Xl) 7) 1)! (2L 21 + 1)! (2 + 1) (21

E

=

1=0

X

Yr,-I(X2)]LM-

-

(6-108) 6.2. Prove

Eq. (6-32).

positive-definite, symmetric matrix A can be diagonalized by a suitable orthogonal matrix T, namely tAT becomes a diagonal di being positive. With the matrix D with its diagonal element Dii use of a transformation x --> y (x Ty), the integral.T of Eq. (6.32) Solution. A

=

=

is evaluated

I

where

as

follows:

exp

(deff)

Though

3

Dy

2

is the Jacoblan

detT is 1 in

Y) (detT)

+ Ts

general,

3

(6-109)

dy

(functional determinant) det(ax/Oy). we

may

assume

dy. preserve the volume element, dx the Since D is diagonal, integration

it to be +1 in order to

=

rately

j

in each

component of y, which reads 1

exp

Therefore

2 we

can now

djyj2 + (ts)j -yj dy

be

performed

sepa-

as

(27r)

3 2

e 2di

(6.110)

di

obtain

N

(27r) d-

3 2

exp( 2di

(6-111)

Exercises

120

N

n,'=, di

It is easy to note that

and

E Jtsfi/dj j=

to detD

equal

expressed

=

det(TAT)

=

detA,

E ,(D-1)jj(!fs)j ( fs)j

as

-

=

j=

-

TsD-lts

9T(TA 'T)ts

9A-1s. Using these results

-

in

Eq. proof. It is useful to generalize Eq. (6.32) for the case where all the vectors and si are d-dimensional. Following the above derivation we get

(6.111) xi

be

can

Z

-Z-

is

=

-

-

leads to the

d

1.,r-,Ax +

exp

where the scalar

(a,, a2,

--.,

x) dx

2

ad)

detA

I

)

exp

2

M-1s),

(6.112)

(inner) product (a b) for d-dimensional vectors d (bl, b21 bd) is to be understood as (a b) -

and

-

=

=

....

i:d Some useful formulas related to this

integral axe collected below. By differentiating both sides of the above equation with respect to the mth component of the vector si,

(xi)m exp

(si)m,

(-2I: Mx 9x) +

we

obtain

dx

d

((A-'s)j)m

(

detA

)

exp

(2 9A-1s)

Further differentiation with respect to

(xi),a (xj),, exp

(

I

TcAx +

-

2

(sj),,

leads

(6.113) us

to

9x) dx

f(A-l)ijJm,, ((A-1S)iW(A-18Wnj +

d 2

exp(19A-1s).

X

detA

Setting

m

=

n

and

f (xi xj) ( -

exp

(6.114)

2

summing

over m

I

7cAx +

-

.

2

leads to

9x) dx

d(A-')jj ((A-1s)i (A-1s)j) +

-

d

X

detA

exp

2

s).

(6.115)

Exercises

121

bl,,,,, with ln 1, 0, -1) a,,,b,, (&,) (M /-4-x/3aYj"' a,,, I rIL) (Im -L: etc. for three-dimensional vectors a and b that is, a, (a,; +iay), \/2 --!-(a,, iay). Here n 0 or I or 2 and -n < [t < r,. ao a, a-, v/2Tn the

case

of d

=

3, let

define

us

product, [a

tensor

a

x

=

=

=

=

-

,

--

=

The scalar

(a b) -

=

=

-

product

-vf3-[a

is

special

a

of the tensor

case

I

bloo

x

that

product,

whereas

=

r,

=

is,

I and

give a vector (outer) product and a second rank tensor. See also Eq. (11.2). The use of Eq. (6.114) leads to the following result r,

=

2

1

[xi

x

xjl,,,,exp

9x) dx

:IAx +

-

2

v/3- &,OJ ,O (A-1)ij

[(A-1s)i (A-1s)j]

+

x

3

2exp 2 gA`s).

X

detA

6.3. Derive

B,,,Pq

a

Eq. (6.60).

npq explicit formula for Bj'.

Solution. The

give

in

hint for its derivation. First

x=

(6-116)

we

r V:r(Yj--j(P)-Yjj(P)), V

is

bit

a

lengthy,

and here

we

recall that

F -r(Yj-j(P)+Yjj(P)), V V

y=i

3

3

VL37'y 7F

Z=

(6.117)

10

Thus the power

XpyqZn-p-q

can

be

expressed

q

P

(7 )n r

XPY qzn-p-q

=

rn

p+q

2

2n-

2

iq

3

E t1=0

X

(yi, (i6))

The power of the k

"+"

(YI -1 (,P))

(k,m)

(Y1jr (j )) =ED L a

(p) E (q) (-1? A

p+q-g-v

spherical harmonics

as

I/

V=O

(y10 (,,))

can

be

n

-p-q.

expressed

(6-118) as

YL km (f)

(6.119)

L

(k,m) where D L

can

be derived

calculated ftom the equation

by using Eq. -(6.10) successively

and it is

Exercises

122

(k,m)

DL

V/47r

=

E LIL2

...

Lk-I

k

xll(C(Li-ll;Li)(Li-l(i-1),ralmlLiim)),

(6.120)

i=1

where

LO

0 and

=

determined

as

Li

=

L. In the case ofTn Lk 1, Li is uniquely 0 there are several possibilities for i, but for rn =

=

=

product of the spherical the following:

the value of Li. Thus the

(6.118)

can

be reduced to

(Y11 (i6))

A+-

(Y,

-1

(f))

p+q-A-v

(Y10(f))

harmonies I

Eq.

n-p-q

(p+q-,p-t/,-I) D(A+"")Dp+q-IL-il E D L(n-p-q,O) 11+V

L

X

Y[t+v li+v(P) Yp+q-A-v

-p-q+IL+v

(f) YLO (i )

product of the three spherical harmonics spherical harmonic by using Eq. (6.10):

The

YIL+z,

IL+v

(i6) Yp+q-tt-71

-p-q+IL+zl

is

(6.121)

-

coupled

to

a

single

(i ) YLO (i6)

E C(IL+v p+q-1-t-7,1; L) C(L'L; 1) L11

X(A+v1-t+vp+q-tz-v -p-q+A+YIL'-p-q+2A+2z;) x

(L' -p-q+21j,+2v L 0 11 -p-q+2A+2v) Y, (6.122)

The above formulas

B npq I.

provide

us

with the

ingredients

needed to derive

7. Matrix elements for

spherical

Gaussians

chapter we show that the generating function introduced in the previous chapter can be used to advantage to derive the Hamiltonian matrix elements of an N-particle system for both the correlated Gaussians and the correlated Gaussian-type geminals. Matrix elements of various physical operators between the generating functions will be tabulated in a compact form. Examples of matrix elements for spherical or primitive Gaussians are given in this chapter and more general matrix cases will be treated in the appendix. We can thus calculate for interaction a many-body system. We elements of essentially any also show that the matrix elements involving the correlated Gaussians become particularly simple in two-dimensional problems. An extenIn this

sion to the matrix element for nonlocal potentials is also presented. We discuss the kinetic energy operator for the relativistic kinematics and calculate its matrix element for the correlated Gaussians as an

example.

7.1 Matrix elements of the

generating

As the correlated Gaussian basis function

can

function

be constructed from

function g (6.19), it is convenient to derive the matrix element between the basis functions from that between the functions This is true even though we use more than one set of coordinates

the

generating

g.

because the transformation of the coordinates

simply leads to

a

change

of the parameters A and s, as shown in Eq. (6.28). It is convenient to use g not only because thereby all types of correlated Gaussians can be constructed in a simplified manner but also because the matrix elements between functions g can be evaluated with ease. Table 7.1 lists formulas for the matrix elements of some basic operators 0

Y. Suzuki and K. Varga: LNPm 54, pp. 123 - 148, 1998 © Springer-Verlag Berlin Heidelberg 1998

7. Matrix elements for

124

spherical

elements, M (g(s; X, x) 101g(s; A, x)), o-Foperators generating functions g of Eq. (6.19). Here we take all vectors d-

Table 7.1. Matrix 0 between

dimensional.

(a

b)

x

and

x is

=

a

N

E,=1 wi xi.

short-hand notation for

tensor

a

product [a

x

b]2,,

A vector

product

defined for three-dimensional

are

XB-1s AB--s. P is A + X, v a and b. B s + s' and y Tpx. permutation operator and the matrix Tp is defined by Px

vectors a

Gaussians

=

=

=

-

=

0

eXP(2!' B-1V)

detB

fvB-1-vMo

X

IdTr(B-'Q) +i B-1QB-1vjMO

aiQx (Q:

symmetric matrix)

a

( X [fV-X

X)

(iv-B-1-v x B-lv) Mo

CX121L

[fvB-lv x (B-1Vj2ttMO -ih&Mo

X X

(7rj

=

-ih

axj

h2

-iA7r

(A:

d 2

(2,X)

MO

a

-

VAy

JMO

symmetric matrix)

L.

(rzL

IdTr(AB-XA)

-i =

Ei(Xi

X

E,, (B-')ij(s'i

x

sj),Mo

7ri)) 2

L2

(fVX

(d X

J(iv-x

J(i7vx P

-

-

-

I)WB-1-s

-

( Ej(B-1)jjZz Sj) I.M0 X

r)

-ih

(fvB-1-v &) Mo

r)

Mi.

=-

(27riv-B-1w)-2

x

exp

r)

(iv-x

x

r)

x

.4

-ihf (r

X

f

1

2iv-B-lw

&) +

(r

AB-lw ivB--Iw

-

(r

I MO ibB-lv) IM,

bB -lV)2 x

(g(s ; A, x) Ig(Fp-s; TpATp, x))

125

7.2 Correlated Gaussians

A4

=

(7.1)

(g(s; W, x) 10 Ig(s; A, x) ,

positive-definite, symmetric matrices. The fxj,..., XNJ, can be integration over a number N of vectors, x carried out by using Eqs. (6.112)-(6.116). where A and X

are

N

x

N

=

leaving this section, we note that the formulation with the generating function, though quite useful and powerful, is still severely restricted in its application to a many-body system by the number of paxticles because of the following properties of the method: Before

1. The number of nonlinear

of

one

basis function is

in the matrix A

parameters contained

N(N + 1) /2. By increasing

particles the optimization hibitively time consuming. of

the number

of these parameters becomes pro-

2. To calculate the matrix elements between the basis

functions,

one

needs to calculate the determinant and the inverse of the N x N matrix B A+ A. The number of operations needed to calculate =

the determinant and the inverse increases

as

N3. The symmetrizaof this calculation N!

the

repetition postulate would require overlap and the kinetic energy and (N(N 1)12)N! times for the potential energy matrix elements, respectively. As the system gets more complex, the number of basis functions needed to represent the wave function increases considerably and

tion

times for the

3.

more

As

was

-

matrix elements have to be calculated.

shown in

Chap. 4,

a

number of random trials

are

probed in the

SVM to select a basis element. To calculate the energy for each trial, the determinant and the inverse of the corresponding matrix B have

computational load mentioned in the second item would become very heavy even for systems containing a relatively small number of particles. Fortunately, when one repeats the calculation of detB and B-1 by changing only one element or a few elements of B, as is often the case in the SVM selection procedure, to be calculated many

one can use

times,

so

the

the Sherman-Morrison formula

involved in the calculations. This will be

[141

to reduce the load

explained

in

Complement

7.1.

7.2 Correlated Gaussians We

assume

form of

that the Hamiltonian of

Eq. (2.1).

an

N-particle system takes

The set of coordinates :Z

=

(xl,..., xN-I)

the

stands

126

7. Matrix elements for

spherical Gaussians

for the relative coordinates chosen to describe the basis function. As a

example of correlated Gaussians we basis function is given by Eq. (6.27):

concrete

that the

fKLM (u, A, x)

exp

(-2I bAx

assume

in this section

IEX12K YLM(ijX).

(fKILIMI (U 7 X7 X-)IOIfKLM(U; A7 X)) I

BKLBK"L'ff X

de--d

f

YL m (e^-) YL, lw,, (, f)

(g(A'eu; X, x) 10 Ig(Aeu; A, x))

*(

d2K+L+2K'+L"

dA2K+LdAj2KI'+L-' (7.2)

X=O,,N,=O' e=jej=1

e"=jeIj=I

As the matrix element

(g(Aeu'; X, x) 10 Ig(Aeu; A, x))

between the

generating functions is given as a function of A, A', e, and e' for various operators by using Table 7.1, one only needs to perform the operations prescribed in the above equation. As will be shown in the appendix, the operations can be done very systematically for many cases of practical interest for arbitrary L. The correlated Gaussiajas with L 0 what we call spherical Gaussians take the particularly simple form in the special 0. As case, K they give a fairly good solution for a variety of few-body problems, we list the explicit for-m of the matrix elements for this case in the following. Because the parameter u of Eq. (6.27) is redundant in this approximation, we denote v'r4-7rfooo (u, A, x) simply as =

=

FA(x)

=

exp,

(-2 Jc'Ax).

(7-3)

127

7.2 Correlated Gaussians

Since this function is

equal

to

g(s

0; A, x),

=

special

a

generating function (6.19), the needed matrix elements given in Table 7.1. The overlap of the spherical Gaussians is given by

(FA' IFA )

(

=

)

A)

in fact

(7.4)

.

The matrix element of the kinetic energy is obtained

(2.10)

are

3 2

(2T)N- I det (A +

of the

case

through Eqs.

(2.11) by

and

2

P

(FAI

-

Tm IFA)

2mi

3OTr (A(A + A) -'A!A) (FA, I FA).

(7-5)

2

The matrix element of the

two-body potential

(FAIIV(ri-rj)IFA)=(FAIIFA)(

is

given by

j)3j V(r)

Ci

2

.1

e-2 C,,r2 dr

(7.6)

27

where I

-

=

w(ij) (A + W) -lw('j)

(7.7)

Cii

w('j) defined by Eq. (2.13). The matrix element of the total potential energy is easily obtained by summing Eq. (7.6) over i, j. As a by-product of Eq. (7.6), we show that the matrix element of Iri rj I' can be easily obtained because then the integral in Eq. (7.6) can be reduced to is

given through the column

vector

-

a

r

-

e

LCT2

2

dr

47r

f

r

a+2

LCr2dr

e- 2

0

a+3

2-x

(2)

x

e -xdx

2

----

C

0 "+3

27r

(2 ) C

2

(a+

where F is the Gamma function. Thus

1

(7-8)

2

we

obtain

7. Matrix elements for

128

(FA'117'i

rjl'IFA)

-

spherical Gaussians

(FA, IFA)

=

2

2

T

Cij

X

where cjj is given by Eq. (7.7). For a spherically symmetric

potential

the

(7.9)

2

integral

W

I(k, c) can

is

a

>

-1

e-

!

CT2

(7.10)

dr

analytically for

a

certain class of

potentials.

If

V(r)

in the form

V(r) then

k

V(r)r

be calculated

given

n(n

fo

=

re-"

=

2-br

(7.11)

expression for I(k, c) becomes possible for -k) by using the following formula closed

an

integer

00

1

ee-ar2-brdr

0

n+I 1

-

T

7F(- I)n

ni

n

Ek=O (n-k')! k! fk gn-k

2 ,fa-

n!

for

for

bn+l

a

> 0

a=O

b>0

(7-12) with

V

fo

go

=

exp

b

(4a) erfc ( 2V/a-

and for k > I

[k121

E V (k

A

k! -

i=O

b

2i)!

k-2i

)

2

=(-I) kH'k-I

A

Here

the

Hn(x)

is the Hermite

complementary

erf (x)

(7.12).

=

(2/V9T f

In

(7.13)

case

error

polynomial and erfc(x) function, where erf(x) is the

e-t2dt.

where

an

1

-

error

erf(x)

fis

function:

See Exercise 7.1 for the derivation of

analytic

evaluation of the

integral

is

Eq. impossi-

ble, one has to rely on a numerical integration. Examples of application of FA(x) to various quantum-mechanical few-body problems and 11.3.

are

presented

in

[811.

See also

Complements

11.1

7.3 Correlated Gaussians in two-dimensional systems

129

7.3 Correlated Gaussians in two-dimensional

systems In this section ments in the

we

case

review the trial

wave

of two-dimensional

function and its matrix ele-

(2D) problems. A real application

of the results in this section will be made to the in

problems In 2D

on

few-body

quantum dots in Chap. 10.

problems

the motion of the

The vector

xy-plane.

study

r

particles

is constrained to the

has therefore two components

r

=

(x, y),

and

for relative coordinates and other vectors introduced

all

expressions 0. The scalar previous sections remain valid by setting z will include variables and over only the spatial integrations products in the

xy

=

components. The main difference between the 2D and the 3D momentum. In 3D the basis function

bital angular eigenfunction

2

of the operators L

,

case

was

is the

taken

L ,:

rlyi-00In 2D L

2 =

as

or-

the

(7.14) L

2

so

Z ,

that

one

of these operators becomes redundant

the fact that the system may be invariant under rotations only. The corresponding orbital angular functions

reflecting

around the z-axis take the form

r'e"mw

=

(X

W,

(M

>_

0),

(7-15)

is, the states are characterized by the quantum number "m". This function, apart from normalization, can be derived from its 3D coun0 (or 6 m and z r/2 in polar coordinate terpaA by setting I that

=

=

=

system). The matrix elements derived for the 3D

case

used because they already include an integration

cannot be

over

directly

the z-component.

One can, however, derive the matrix elements in a very similax way by using generating functions and exploiting the simplifications present in the 2D

function.

the

The first step toward this is to construct a generating Similarly to the 3D case, we assume a trial function, by using

global

case.

vector

fm(u7 A7 x) where the

x

x

representation,

=

(V1

+

in the form:

iV2)' exp

I -Je' A x

(_2

,

(7.16)

is the vector of relative coordinates in 2D and v, and V2

and y components of the vector

are

7. Matrix elements for

130

spherical Gaussians

N-1 V

(7.17)

Uixi.

Note that the

complex conjugate of fm (u, A, x) is an eigenfunction of L, with eigenvalue -mTo derive matrix elements, one can use a particularly simple generating function for f,,, (u, A, x): dr"

f (u, A, x)

--

..

dtra

g(s, A, x)

(7.18) t=O

with

g(s, A, x)

=

exp

1-2

- CAX +

where the 2D vector sj (j vector (tuj, ituj). Note that

=

*1

+

I,-, N

iV2)

-

1)

(7.19) is defined

by

a

*

complex 2t-eui Uill

they satisfy si sj 0, si sj'3 generating function remain valid as listed in Table 7.1 by substituting d 2 and assuming 2D vectors. By using the matrix elements of the generating function all the necessary matrix elements can be easily calculated by carrying out the differentiation prescribed by Eq. (7.18). The matrix elements for some basic operators -

=

-

=

The matrix elements of the

=

are

collected in Table 7.2.

Table 7.2. Matrix elements A4 ...... B is equal to A+ X. A is defined in same as

be

defined in

changed

0 If,,) for two-dimensional

Eq. (2. 11). Q, R,

Eqs. (A.2), (A.9), and (A.18), integral I is defined in Eq. (7.10).

to 2. The

0

Mram' M,,,J IV

P2

Ei=l 2mi IiA7r

-

T,,.,n

..

.,

with

Mm

(27r)N-1 detB

1(2p)m

+ mQ)MmJmm, -lh2(R 2 P

=

L;,

V(J ri

MMmJnm' -

ri 1)

(27r)'V-'-c(7nI)2I5mM, J:M detB

case.

p, p, -y, -y, c are the but the factor 3 in R must

n=O

(2#)m-'(-y-y')' (m-n)!(nl)2 1(2n+1,

c)

7.4 Correlated

7.4 Correlated We

the form of

(Irl,

...

Gaussian-type geminals N-particle system now takes single-particle coordinates j

that the Hamiltonian of the

assume

Eq. (2.2). We

the

use

=

in this section. The transformation matrix U defined in

rN)

Eq. (2.4)

131

Gaussian-type geminals

is

now

redundant

or can

be set

equal

to the unit matrix.

The basis function is chosen to be the correlated

Gaussian-type geminal of Eq. (6.26). The function is characterized by three parameters. The matrix A describes the correlation among the particles, the diagonal matrix B determines the spread of the single-particle wave(RI, RN) give the centers of the packets. This packets, and k type of basis function is employed in molecular physics and nuclear cluster models. The permutation P of particle indices transforms the coordinates as defined by Eqs. (2.26) and (2.27). This transformation changes the basis function to =

...,

(TpATp, TpBTp, TpR, r),

Pf,,(A, B, R, r) where

use

stands for

p-I Thus the

is made of the relation

fnq,,, nq,-2 PI

P2

1

2

(7.20)

'n

,

nq13 ...

...

, ....

N

permutation acting

=

nqN, ,

PIV

Tp-i (Tp)-' for nq,3) nq,2, 1

) (q, on

2

and

Tp-n

N)

...

q2

Tp-

=

qN

...

the basis function

just leads

to the

simple transformation of the parameters, A, B7 R, and n and still keeps the form of the basis function invariant. It is not nice, however, that the value of n changes under the permutation. The integral needed to evaluate the matrix element with the correlated Gaussian-type geminal is 3N dimensional and of multi-center type. Such integrals are extremely hard to calculate and to handle. See, e.g., [82, 831 for some developments made for those multi-center integrals which appear in molecular physics. To avoid the complication, a few simplifications are introduced in practice. For example, only one pair of particles is allowed to be correlated in each basis function. This is equivalent to assuming that the only non-vanishing elements of the matrix A are, Aii = Ajj correlation between the ith and

expf-aij(ri _rj)2 /21.

Another

=

aij and

Aij

=

Aji

=

-aij, if the

is taken into account

jth particles simplification

is to

use

by only primitive

0. Primitive Gaussians Gaussians, that is, the basis function with n yield solutions of good quality for few-electron systems. In this section we calculate the matrix element in the primitive Gaussian basis =

7. Matrix elements for

132

spherical Gaussians I

fo (A, B, R, r)

=

=

allowing the

most

exp

-2

exp

2

I

FAr

-

2(r

-

R)B(T

-hBR) g(BR; A

general type

R)

-

B, r),

+

(7.21)

of correlations. The formulation pre-

sented here will be found to be very simple and lead to compact results for various matrix elements. The matrix elements with higher angular

momenta, when needed,

be obtained from the matrix elements

can

generating function by straightforward but tedious differentiaalgorithm for a systematic evaluation of the differentiation is presented in Appendix A.3. The overlap matrix element is readily available from Table 7.1. It in the

tion. An

reads

as

MG

(fo (A!, B', k, r) Ifo (A, B, R, r))

=

3 2

exp

detC

2'DC-1v 2RBR 2kB -

(7.22)

-

where

C=A+B+X+B',

v

=

BR+ B'k.

Note that formulas derived in this section metric matrix B

or

are

(7.23)

valid for

a

B' provided that A + B and A! + B'

general are

sym-

positive-

definite. The matrix element of the Idnetic energy is also available from Table 7.1: N

(fo (A! B'; k 7

h2 =

2

JKI ((A

I? P'

2mi

+

I fo (A, B, R,

B)C-'(X + B)A)

-

VAyjMG

(7.24)

with y

=

(X + B)C-'BR

where A is

a

-

(A + B)C-'B'k,

diagonal matrix with Aii

=

I/mi.

(7.25)

The matrix element of

the center-of-mass Idnetic energy is calculated very easily as -well. As Eq. (2-10) shows, it is calculated by the above formula with a shnple

7.4 Correlated

modification: The matrix A is all i and

now

to be taken

we

make

Aij

:--

1/?n12

...

for

N

one-

and

two-body poten-

following relation

of the

use

(fo (W, B/I k, r) I V (I iv- r =

as

j.

To calculate the matrix element of both tials

133

Gaussian-type geminals

B, R, r))

S 1) 1 fo (A,

-

f V(x) (fo (A!, B1, k, r) IJ(,Cvr

-

S

-

x) I fo (A, B, R, r)) dx, (7.26)

where iv-

(WIi

:--

...

i

WN)

is

an

auxiliaxy parameter

and S is

a

3-

dimensional vector. Substituting the matrix element of the J-function leads to

Eq. (7.26)

in Table 7.1 into

(fo(W, Bf, k,,r)IV(Ifvr

27r)

=MG

-

2

Sl)lfo(A, B, R, r))

expf

V(X)

C

C _

2

(X + S

_

VC-IV)2ldX

17

0,0

FTCVS C

1CS e_2

2f

-I

V(x) x e-!i

CX2

(ecx

-

e-

csx)dx,

(I 0

(7.27) where

c-1 =,W-1w were

and

s

=

jW-1v

-

(7.28)

S1

introduced.

two-body matrix elements are calculated in a unified way with an appropriate choice of w. The matrix element of the one-body potential, V(Iri SI), can be obtained by N). If V(x) takes the form of Eq. (7.11), choosing wj Jij (j then the above integral is obtained analytically for n (n > -1) As the most important application of this formulation, we give below the matrix element for the Coulomb potential: We show that both

one-body

and

-

=

=

-

1

(fo (X, BI k' r) 1 I

Iri

-

S1

1 fo (A, B, R,

( F?)' c

erf

MG S

where c-' is

now

defined

by

(C-1)jj

(7.29) and

s

is

given by I (C-lv)i

-

S1

-

7. Matrix elements for

134

The

the

matrix element

two-body

by

same manner

the

the matrix element of as

Wk

=

-

Coulomb

the substitution of c-1 s

J(C-'v)j

=

tor e-P'

can

also be obtained in

of

exactly

Eqs. (7.27) (7.28). needs to choose w one only SI) rj the of the matrix element 1, E.g., rj 1, can be calculated from Eq. (7.29) With use

V(Iri

Jik Jjk (k potential, 1/ Iri

:--

spherical Gaussians

-

and

To derive

-

-

(C-1)jj + (C-l)jj (C-1)jj (C-1)jj (C-lv)jl. When V(x) takes the Gaussian form

-

=

-

-

and fac-

2, the matrix elements for both the central and the spin-orbit

potentials

can

be

expressed

particularly simple

in

forms:

(fo(X,Bf,k,r)je-P(' '_-r)2 Ifo(A,B,R,r)) -9

c

c+2p

)

2

CP

expf

-

c

(fo (A!, Bf, k, r) I e-P(fVr) 2(for

+

x

2p

(iV-C-1V)2j.

(7.30)

p) I fo (A, B, R, r)) Ii

=

-ih( W-lv

X

&)-MG (

C

c

+

CP

2

2p) eXpj

c

+

2p

(CVC-1V)2j. (7-31)

It is clear that the above formulation

N-body

matrix elements

as

applies

to the calculation of even

well.

7.5 Nonlocal

potentials

In this section

show

simple example of the extension of the calculational technique to nonlocal potentials. The application of nonlocal potentials will be presented for positronic atoms in Sect. 8.3 and for the nucleus 12C iTj Complement 11.4. The potential is assumed to be of separable form we

a

N

E ki

V

(Ti

-

rj)) (W. (ri

-

Tj)

(7.32)

a

with

a

Gaussian form factor

O a Or)

-

=

This form is to other

e

-21

ar

2.

(7-33)

quite useful in many practical cases, but generalization is straightforward by using the same trick as for the

cases

7.5 Nonlocal

that is

potential functions, function

J(ri

-

rj

-

135

potentials

by substituting the function

o,,

by

a

delta

r).

The first step of the calculation of the matrix elements of the above potential is to substitute the relative coordinates x by a new set of

Jacobi coordinates Y fY1; --- YN-11. The Jacobi coordinates y are the from obtained original set of coordinates x in such a way that yj =

=

,ri

The matrix of the

(see Sect. 2.4).

-rj

corresponding transformation

y=T (k)X,

(7.34) 1, is defined in Sect. 2.4. The kth (k) T is defined in such a way that the first

det(Ox/Oy)

whose Jacobian is in

permutation

deriving equal

Jacobi coordinate is

to ri

=

-

rj.

The next step is to show the matrix elements for the generating function (6.19). The matrix element of one term of the potential reads as

(g(s'; X, x) I

o,, (ri

-

rj)) (W,, (ri

-

rj) Ig (s; A, x))

(g(ts; tXT, y) IW,,,(yj) (W,,(yjjg(ts; tAT, y)),

(7.35)

integration has to be carried out first over yj in both sides and then over the remaining coordinates, yj's. We use the same notation y to denote these remaining (N 2) variables, as well. To carry out the integration implied in Eq. (7.35), we introduce the following where the

-

notations: -

B:

an

row -

b:

(N

-

2)

x

(N

-

2)

matrix obtained

and the first column of the matrix

an

(N

-

by suppressing tAT.

2)-dimensional vector I (TAT) 12,

the first

(TAT) I N-1

-

bi: the first diagonal element of the matrix (TAT), i.e., (TAT),,.

-

t:

-

tj: the first vector

a

set of

(N

-

2)

vectors

j(t8)2,

---I

(tS)N-11-

(Ts) 1.

corresponding to the bra side are introduced in exactly the same way and distinguished with a prime symbol from the quantities of the ket side. By separating the yl-dependence explicitly from the generating function g as The notations

g(Ts; TAT, y) g(t; B, y) exp and

by using

the formula

(-2 bjy2 (6.32)

1

by. yj

one

obtains

_

+ tI. yj

(7-36)

7. Matrix elements for

136

Gaussians

spherical

(w,, (yJ lg(i s; i AT, y)) i 2

(2T

(2d

exp

d

t2

g

(t

-

d

bti; D,

y),

(7.37)

where 1

D

d=a+bl,

B

=

-

bb.

(7.38)

d

As this function is again a generating function, the integration over the remaining variables y is just the overlap of the generating functions, and from Table 7.1

one

(9(8'; A!, X) kPa (Ti

obtains the final result

-

Ti)) ((Pa (Ti

ddI det (D -+D 1)

exp

rj) Ig(s; A, x))

3 2

(27r)N

X

-

as

-

)

I 1 Iti2 + 2d' t/ 2+ iTo (D + D) -1vO 2

(2d

(7.39)

1

with vo =t-

Ibt, + t'

I -

d

&

b't'l.

The above result becomes Gaussian with L

(FAd Wa (ri

-

=

(7.40)

paxticularly simple for

0 used in Sect. 7.2 and reads

TA) (Wa (?'i

-

ddIdet(D + DI)

Ii) IFA)

)

(7.41)

To calculate the matrix element for nonlocal

factor,

(J(y,

-

we

as

32

(27r)N

form

the correlated

note from

Eq. (7.36)

potentials

of an

arbitraxy

that

r) lg(i s; i AT, y))

g(t

-

br; B, y) exp

which leads to the

general

(g(s'; A!, x) 1,5(,ri

-

rj

(-2 blr2

+tl-r

result

-

r)) (J(ri

-

rj

-

r) Ig(s; A, x))

(7-42)

7.6 Semirelativistic kinetic energy 3 2

(2r)N-2 det (B +

x

B)

(_2Ibir2+tl-r

exp

137

-

Ib' rt2 + t/ rf+Iij (B + B') -1v .

1

2

1

2

(7.43) with v

=t- br

+t'- b'r".

By introducing the

(7-44)

short-hand notations

ti .Z

W

C

-

b(B + B)

-1

(t + iV)

=

I

ti b,

-

6(B + B')-b

-

(B + B)-'(t + t)

-6(B + B")-lb'

=

1

41(B + B)-lb Eq. (7.43)

can

be

expressed

(g(s'; X, x) I J(ri

-

rj

-

V,

-

(7.45)

61 (B + B') -Ib'

in terms of g in

compact form:

r')) (J(ri

r) Ig(s; A, x))

-

rj

-

3

N

2 (2 det(B + i ')

X

2

exp

-

2

(t + t) (B + B)

-1

(t + t)

g(W; C' Z).

(7.46)

7.6 Semirelativistic kinetic energy This section shows the calculation of the matrix element of the semirelativistic Idnetic energy. This will be needed in the

nuclear systems among others. See Chap. 9. We assumed the nonrelativistic Idnematics in

application

Chap.

2. The

to sub-

single-

Idnetic energy T is then related to the momentum p by p 2/(2m). In the relativistic Idnematics it is replaced by T

particle T

=

V4c__2p2+,rn2c4

=

mc2. The speed of light c is set to unity and the term, -mc2, is dropped unless otherwise stated as it just shifts the -

138

7. Matrix elements for

energy

expectation value. The kinetic

spherical Gaussians energy

we

consider takes the

form IV

T.r

I"

=

rIzP12 +Ira?

(7.47)

z

The evaluation of the matrix element of the operator (7.47) is never trivial, because the separation of the center-of-mass motion requires

special care.

The contribution of the center-of-mass motion is removed

for the nonrelativistic

case

in Sect. 2.1

by subtracting

the center-of-

kinetic energy from the Hamiltonian. This prescription led us to the expression (2.10) for the intrinsic kinetic energy, which, as it mass

should, does not contain any dependence on the total momentum -r, IV. However, this method no longer applies to the present case and must be replaced by a more general procedure. We assert that the sought procedure is to evaluate the matrix element in the center-of-mass system, that is, in the system of IV :=

,7r,v

E pi

(7.48)

0.

i=1

Note new

that, when applied to the nonrelativistic kinetic energy, this, procedure reduces to the previous prescription of subtracting

the center-of-mass kinetic energy from the total kinetic energy as expected. This is easily seen as follows: By substituting Eq. (2.9) into N

(1/2) ENJ j= E3=,Aij-7ri--rj with Aij being defined by Eq. (2.11). (The center-of-mass kinetic energy was subtracted from the beginning in Eq. (2.10), so that the suffices i and j go up to N 1 and Aij was defined for i, j :! , N 1. In Tnr

=

i:N p2/ (2mi), j= I

i

we

obtain Tn,

=

-

-

the

case

where the center-of-mass kinetic energy is included, it is not see that i and j take I to IV and Eq. (2.11) is still valid for

difficult to

requirement (7.48) then restricts the sum over practice instead of up to N. Thus the matrix j element of the operator T,,, evaluated in the center-of-mass system is equal to that of the intrinsic kinetic energy of Eq. (2.10). Now we will show a method of calculating the -matrix element of T,

(i, j

=

i and

11

....

N).)

up to N

The

-

I in

in the center-of-mass

system in

two

steps. The first step is

to express

the operator in terms of the operators defined in the relative coordinates. As Eq. (2.9) shows, the single-particle momentum operator pi can use

be

expressed

in terms of the N momenta 7rj (j x defined by the tran

the Jacobi coordinate set

N).

=

r-ma

i

-n

If

we

matrix

7.6 Semirelativistic kinetic energy

139

(2.5), the momentum PN becomes just --7rN-1 thanks to the condition (7.48). This peculiarity was already noted in Sect. 2.4. Note that none of the other momenta takes such than

one

-7r's. Let

denote this

us

a simple form; they contain more particular Jacobi coordinate set x, the

and the momentum 7rIv_1 defined in this co(N) Ov) I and -7r N_ respectively. Obviously we can

corresponding matrix Qj, as

X(N),

1)

other sets of Jacobi coordinates

ordinate set

(N

define

-

each of which

J

x(k) (k

1,

=

1

acting with the cyclic permutation (1, 21 k-times

on

2.4 and

Fig.

tion

be obtained to the

original Corresponding

2.2.

froM

permutation (1, 2, of the

U(1) U(3) J 1 7

to each set

Eq. (2.4) defines TT(". i

to

IV)

=

...'

masses

U(2) i

from

-

a

N)

and

so on.

same

Likewise,

1), by

2

...

N

3

...

1

x(M. See

also Sect.

linear transforma-

It is easy to

and at the

mi,...' miv..

,

X(k)

(2 see

the N column vectors of

by rearranging

permutation

...,

pattern of the Jacobi set

analogous

N

to the relative coordinate set obtained

corresponds

the

...'

U(1) i

can

N)

U(i

time

U(2)

that

according by cyclic

can

the

be obtained

As the transformation between

and relative coordinates is

the

single-particle always given in the form of Eq. (2.4) for any Jacobi set X(k), the corresponding transformation of the single-particle and relative momenta is also given as in the form of Eq. (2.9): N

E (U(

Pi

i

))

7r,(k)

i

=

3

ji

1,

...'

N).

(7.49)

i=1

we

Using the special form of the matrix U(k) and the condition (7.48), following useful relation

obtain the

Pk

=

(k) -7r.-i

(k

=

1,

...,

N).

(7.50)

That is, the kth single-particle momentum is equal to the negative of 1-th relative momentum defined in the kth Jacobi coordinate the N -

set.

Therefore,

energy

(7.47)

with the

can

be

help of Eq. (7.50) the semirelativistic kinetic effectively replaced in the center-of-mass system

by N

T.r

)2 +M2 _(7rN-02 J2 Mi' MI (')

+

Note that this operator has

be paid is that

one

(7-51)

no cross terms such as -7ri--7rj. The price to has to transform the coordinate systems conforming

7. Matrix elements for

140

W

to 7rN-,. There is

work with

can

spherical Gaussians terms when

difficulty in evaluating the cross

no

one

definite set of the relative coordinates. That is the

a

followed that route for the nonrelativistic kinetic energy reason why in Sect. 2.2. In the case of the sen-lirelativistic kinetic energy the cross we

term has to be avoided

will be shown below.

as

The second step is to show how to evaluate the -matrix element of the operator (7.51). One has to calculate the matrix elements term by show

method

term. For

brevity

Gaussian

FA(x)

set of the

Jacobi coordinates X(N)

we

of

Eq. (7.3).

Let

N-

only

=

simplest correlated

for the

x

denotes the last

jX1'...' x1v-11.

To calculate the

us assume

(7r(i) J2 +,rn?,

matrix element of nate

a

we

that

have to transform the coordi-

Z

system conforming to the ith Jacobi

set. This

can

be achieved

by

using the relation X

where last we

=

V(i)X(i)

V(')

row

is

(7.52)

1

an

(N

-

1)

and coWmn of

x

(N

-

1)

matrix obtained

U(N) (U('))-l. By using

by omitting

the

this transformation

have

(FA, (x) I

(7r(')

N-I

)2

+

Ta2i IF ,(X))

(detV(') )3 (FA,(i)(x('))IV(,7r(') N- 1)2+Ta,21FA (,)(X(i))), where

(detV('))'

is

Jacobian

a

corresponding

to the

(7-53)

change of

inte-

variables and

gration

A(')

=

A!(')

00AV('),

=

00WO).

The kinetic energy operator and the relative coordinates of the lated Gaussians are now expressed in the same coordinate set.

To cope with the square root,

we

(7.54) corre-

go from the coordinate space to

the momentum space:

(FAf(,)(X(i))l

/(7r(i)

N-I

)2+Ta3jIFAW (X(i)))

ff (FA,(i)jk')(k'j (-7r'(') 1)2+mj2jk)(kjFA(i))dkdk, IV-

where k as

(k" I k)

(7.55)

(27t-)-2R-'V-1-)6i 0 is normalized kiv-11 and (xlk) Iki of the correlated Gaussian The Fourier transform J(k -k). =

. ....

7.6 Sen-Arelativistic kinetic energy

and the matrix element of the square root operator a very simple form:

( kIFA)

(xlk)* exp

=

=

(detA)

-,)2 fixj(v'

(k'I

+

-

2

(-2 FcAx)

V/ (w

=

(7.56)

Vh 2 k,2v-

=

+

into

j

I

+

;j J(k

Eq. (7.55),

-

k').

(7.57)

one can

reduce the

M2 FA (x))

(detV(') )3 (detA(')detX('))-32 x

=

dx

,

mj2 I k)

_1)2

be written in

FA- (k),

By substituting these expressions integration over k as follows:

(FA, (x)

can

(FA,(j)

(k) I

-i

Vr(7r,(i 1)2)2

+

M3 mj2i IFAM

(detV('))3(detA(')detA!('))--:32i x

(FA,(j)

(k) IJ(klv-l

-i

-

(k))

f vh2q2

q) IFA(j)

-,

+

Ta2i

(k))dq.

(7.58)

To calculate the matrix element of J(kN-I-q), werewriteit

q)

with

make

141

an

use

I x (N

auxiliary

-

1)

one-row

matrix Cv

of the formula in Table 7. L Then

(FA, (x) I

V (7 (Vi r

1

)2

+

M

if 2

27r

e-2Iciq2

(0,

as

J(iv-k-

0, 1) and

obtain

i2 I FA (x) )

(detV(') )3 (detA(') detA! x

we

=

(FA, (j)

vh2q2

+

-1

(k) I FA(j)

-1

(k))

Mi2 dq 3

(FA, I FA) f (ci, mi)

(2-x)

(det(A

IV-

+

A)

f (Ci, 7ni),

(7.59)

with

Ci

(f,7(i)A(A+A!)-'A'V('))

where the function

f

is defined

by

N-1

N-1,

(7.60)

142

7. Matrix elements for

spherical Gaussians

(2v) X je-2-Ixq2 2

Ax M)

X

47r

( ) 27-1

and

use

a2

j,)O

h2 -+M2 dq I

(FAIIFA) =

-=

\//-h2q2 + M2 q2 dq,

(7-61)

0

is made of the fact that the

with respect to the

2

e-!! xq

change

overlap has the following property

of the Jacobi coordinate set:

(FAI(x)IFA(x))

(detV(') )3 (FA,(i) (x(')) IFA(i) (x('))) i

(detV(i))3 (detA(')detA'())-i (FA,(j)-i- (k)IFA(i)-i (k)). 2

(7.62) The

overlap (FA, I FA)

is

explicitly given by Eq. (7.4).

143

Complements 7. 1 Sherman-MorTison

fonnula

To show that the Sherman-Morrison formula

vantage let

in

us use

selecting

a

[14]

can

be used to ad-

basis element from among many random trials, (4. 1) or Eq. (7.3) as the basis

the correlated Gaussians of Eq.

functions. The matrix elements

Aij or, equivalently, aij are nonlinear and of the they are related to each other through Eq. basis, parameters (2.25). As is shown in Sect. 7.2, the calculation of the matrix elements, (FA, I FA)

and

(FA, I HI FA), requires

and inverse of the matrix B Let

that

=

the evaluation of the determinant

A + X.

optimize the symmetric matrix A of nonlinear paxameters by changing only one element, say Ak1 Alk, or aij (j > i), but by keeping all other parameters unchanged. Instead of changing all of the nonlinear parameters randomly at once, we change one particular element randomly and then proceed to other elements step by step. The latter type of optimization of A is certainly us assume

we

attempt

to

=

a

very restricted way, but in this

the computer time

case

required for tremendously reduced, as will useful in selecting a successful

the evaluation of the matrix elements is be

seen

below. And it is

actually

very

candidate from among a number of random trials. We see from Eq. (2.25) that changing only one element aij to aij + A produces a change in A as follows: A

--+

A+

where the

(2.13). k,

Alk

--+

-

is just

OPOP

a

(and 1, k) Alk + A) can e(')

as

e(')

-

1)

x

(N

-

1) matrix,

Eq.

whereas

AN

,

=

follows:

A

where

(N

is defined in

-

e(k)

A+ 1 +

an

Oi)

hand, changing directly only Alk of A as AN AN + X (and be achieved by introducing (N I)-dimensiOnal

element

unit vectors

is

column vector

number. On the other

I

A

(7.63)

I)-dimensional

Note that

Oi) 0A the

(N

Aw(0w(ii),

+

e(l) eo(k)

(7-64)

Jkl

is defined

ui and vi stand for

by

(N

-

given by Eqs. (7-63) and

(e('))i

1). By letting I)-dhnensional vectors, both of the changes (7-64) are in general expressible as =

Ji, (i

N

-

P

A

--->

A+

Aiuigi,

(7.65)

Complements

144

where p is either I or 2. As B is equal to A + leads to the

following

X,

the

change B,

of A

as

given by Eq. (7.65)

modification of

P

B

---+

B+

(7.66)

Aiuigi.

Therefore the calculation of the matrix element for the above

change

of A results in the calculation of the inverse and determinant of the

special form of matrix, B + a, Aiuigi. When the modification is given by just one term of the form AuO, the Sherm an-Morrison formula can

be used to obtain

Aub)-'

(B

+

det

(B + Aub)

B-1

-

-AB-1u,6B-1,

1 + AbB-lu

(7.67)

and

(I + A,5B-1u)detB.

(7-68)

See Exercise 7.2 for the derivation of the Sherman-Morrison formula.

advantage of these formulas is appaxent: By knowing B-' and detB one can easily calculate the right-hand side of the equations, and the A dependence is given in a very simple form. To change A, therefore The

there is

no

need for the evaluation of inverses and determinants of the

modified matrix B

(which would require (N

get the desired results by

_

1)3 operations),

but

we

simple multiplication and division. When the modification of B is given by Eq. (7.66) in fiL11 generality, then the inverse and determinant can be calculated by using the Woodbury formula [141, which is the block-matrix version of the Sherman-Morrison formula. If one wants to change a few of the aij's or one-column (and one-row) elements of A at the same time, the summa ion in Eq. (7.66) has to be further extended appropriately. a

Exercises

145

Exercises

Eq. (7.12).

7. 1. Derive

Solution.The the

integral

case

as

of

a

=

0 is

1 00rnCar2-brdr

dn 1

(_I)n x

case

of

a

>

0,

we

may

get

dn

(-I)n

=

0

By putting

In the

simple.

follows:

=

dbn 2

bl(2,Va-),

1000e-ar2-brdr I-exp ( ) erfc( \,Fa

dbn

V

b

4a

a

the above

2

(7-69)

-

equation becomes

00

fo

rne-ar2-brdr

=

V,-(_I)n

(

1

2

- fa- )

n+1

n

nt

k=O

(n

-

k)! k!

A (X)

gn-k (X) ,

(7-70)

where

fk (X)

=

A (X)

=

(_X2) (eXp (X2))

eXp

(k)

eXP(X2) (erfC(X))(k).

(7.71)

fk (x) defined Eq. (7.13). Remembering that the

It is easy to show that

above is

in

Hermite

not

(n)

(-I)n eX2 (exp(_X2)) difficult to check that gk(x)

.(X)

=

7.2. Derive

and

can

(erfc(x))

be

equal to the one given polynomial is given by (1)

expressed

_X21 V/,-X-,it is -

=

as

-2e

in

Eq. (7.13).

Eqs. (7.67) and (7.68).

Solution. Let X represent u,&. Then the inverse as follows:

(B + AX)-1

may be

calculated

(B + AX)

-1 =

(I + I\B-'-X) -'B-1 CO

=

j:(-A)n(B-IX)nB-1.

(7-72)

n=O

special form of X, XB-'X reduces to cX, where the constant factor c. is given by OB-'u. Therefore repeated use of this relation leads to the follwoing result: Because of the

Exercises

146

(B -I.X)n B-1

B-'(XB-'XB-'X

=

d'-'B-'XB-1

=

By substituting

this result into

(B + AX)-' which is

nothing

=

......

(n

Eq. (7.72),

>

we

B-'XB-17

-

(7.74)

Eq. (7-67).

but

given by Bij

P(A)

obtain

I+Ac

+ Auivj, let

us

(B + AX)

=

-

=

ao +

aj.X +

-

-

+

-

(i, j)

with its

suppose that the determinant is a The function P(A) is a polynomial

P(A) det(B+AX). degree (N 1) and can be expanded

function of A:

of at most

(7.73)

1).

A

B-1

To calculate the determ In ant of the matrix

element

B-'X)B-1

as

follows:

aN-O:I F-1,

(7-75)

where the coefficient ak is calculated by k!p(k) (0). The rule of dif0 ferentiating determinants leads us to the conclusion that ak =

for k ao

=

2 because of the

>

P(O)

=

special

form of the matrix X. We have

detB. The coefficient a, is obtained

as

B1,

B12

B, N-1

V1

V2

VN-1

Biv-, I

BN-1 2

BN-1N-1

follows:

N-1

Ui

a,

N-1 N-1

IV-1 N-1

E Y uivj,6ij

E T ujvjdetB(B-')jj

i=1

i=1

j=1

j=1

(,DB-1u) detB.

(7.76)

Aij is the (i, j) cofactor of the matrix B and use is made of the detB (B-1)jj. Thus P(A) is eq ial to (I+ADB-'u) detB, relation Aij Here

=

which is what

we

7.3. Calculate the

want to derive.

one-body density matrix for the generating function

g: Pi W,

r)

(g(sf; X, x) IJ(,ri

-

xN

-,r'f)) (,5(,ri

-

xN

-

r) lg(,s; A, x)).

(7.77)

147

Exercises

(2.12) shows,

Solution. As Eq. W The

ri

-

can

xN

be

expressed

as

EN-I 1=1

argument made for the nonlocal potential in Sect. 7.5 in exactly the same way. The can, therefore, be applied to this case only necessary change is to replace w('j) with 0). The density matrix When the wave function pi (r, r) takes the same form as Eq. (7.46). has the proper symmetry for a system of identical particles, the onebody density matrix does not depend on the suffix i.

w, xj.

Reproduce the nonrelativistic kinetic energy formula (7-5) by using the formulation presented in Sect. 7.6. 7.4.

Solution.

By using Eq. (7.50), the matrix element of the nonrelativistic

kinetic energy operator in the center-of-mass system becomes IV

N

2

(FA'(-X)JE

IFA(X))

2Tnj

=

(FA, (x) 11:

(i)

(7rN-l)

IF",(X))

2m,

3h2

(7.78)

(FAI IFA)

2mici

3h2 / (2mx) for the nonrelativistic kinetic energy is f (x, m) obtained by replacing Vlfh-2q2 + M2 in Eq. (7.61) with h2q 2/ (2m). To perform the summation over i in Eq. (7.78), we need to know the special matrix element M9 N-1: k

where

=

N

VM

(U(N) )kI (TT(i)

-

us

vectors of

Uj(N)

TnI , M2 ,

....

(1, 2,

N)

can

0) i

recall that

...,

mv

can

Uj and

EE

(7-79)

i

kN-i

Let

-I

IN-I

be obtained same

time

with the

i times. Rom this construction it is easy to

be obtained from

constructed from

N)

Uj('

(N)

in

Uj'

but

the column vectors. Then

the N column

by rearranging the masses the operation cyclic permutation

at the

according to

by rearranging

exactly

the

see

that

same manner as

by rearranging the row obtain (see Eq. (2.6))

U(') i U

M is

vectors instead of

we Mi

for

1: k i

for

I

M12---N

UW

(7-80) I N-1

-(I

'i

-

) M12---N

=

i.

Exercises

148

Using

this result in

0 for k

Eq. (7.79) and noting the relation

N enables

VW siimma

IV

i

n

3h2 -

2mici

over

3eT 2

which

was

(

Eq. (7.78)

(A(A

+

X)

can

easily

j(kv)

U

as

(7.81)

(UJ)ki

be done to obtain

-'A!A)

being

(7.82)

defined

kinetic energy from the total kinetic energy. This exercise serves as an indirect evidence for the

formulation

-

by Eq. (2.11). This agrees with Eq. obtained by explicitly subtracting the center-of-mass

with the matrix A

(7.5),

i in

I

to obtain the desired matrix element

(U'(V))ki

-

kIV-1

The

us

E'V I=

given

in Sect. 7.6.

validity of the

8. Small atoms and molecules

examples for the application of the method to atomic and molecular systems. The interaction between the charged particles is the Coulomb force. The long-range character of this force makes the solution of the few-body problems difficult, especially in the case of scattering. We restrict our attention to bound states, where This

chapter

contains

many different methods have been elaborated in the

These calculations

provide an

excellent

past decades.

possibility to test the

of our method. Relativistic effects in atoms

perimental precision of today, which calls

are

efficiency

withi-n the reach of ex-

for very accurate theoretical

calculations.

8.1 Coulombic

systems

The systems of charged by the masses (MI jn2 ,

particles

can

be characterized and classified

mN) and the charges (qj,q2,...,qN) of distinguish systems formed by either equal (unit) or unequal charges, and depending on the masses of the particles one can classify the systems as adiabatic and nonadiabatic ones. ITI the unit charge systems of more than two particles the constituents form a molecule and the binding energy depends only on the mass ratio(s) of the particles. Atoms are good examples for systems with unequal charges. The distinction between the adiabatic and nonadiabatic cases is dictated by the possibility of a simplified treatment in the former case. In the adiabatic case the masses of a group of particles are considerably heavier than those of the rest. The classical examples are the molecular ion (see Complement 8.2). In these H2 molecule and the H+ 2 cases the electrons move faster, while the protonic frame may rotate and vibrate by moving considerably slower. This physical picture is expressed in mathematical form as the Born-Oppenheimer approximation, where the electronic motion is first calculated by assiimin the constituents. One

....

can

Y. Suzuki and K. Varga: LNPm 54, pp. 149 - 176, 1998 © Springer-Verlag Berlin Heidelberg 1998

8. Small atoms and molecules

150

form

CkA

JeXP

2

i AkX) jVk 12K+L YL

M

(f,-I") X Slus

k

(8.1)

UkiXi

Vk

The operator A is introduced to impose proper symmetries on identical particles (antisymmetry for fermions and symmetry for bosons) of the system. In most calculations the index K is assumed to be zero or at most zero or one. In the case of the PS2 molecule of Sect. 8.3, K is set

equal

to

zero.

The details of the calculations

can

be found in

some of the system presented in this chapter. The vari[33, 84, 851 ational parameters included in each basis function are the elements of

for

the -matrix

Ak and the coefficients

Uki, which define the

vk. Since the Hamiltonian used in this

chapter

global

vector

commutes with the

spin operator, the variational trial function can be chosen to 'have a definite spin value S. The value of S influences the symmetry of the orbital part of identical particles. Therefore, possible S values 'have to be tested in general to obtain the ground state. For treating the adiabatic system of small molecules in Sect. 8.4, we use combinations of the generating function g itself as the variational trial function.

8.2 Coulombic

three-body systems

8.2 Coulombic

13-16

figures, that the solution of

lem is

one

151

three-body systems

the Coulombic

three-body prob-

of the most useful benchmark tests to compare different

methods. The accuracy pursued in Coulombic cases is not of purely academic interest, but highly motivated by the high precision of the For

experiments.

example,

the fine-structure

splitting of the

state of the Li atom has been measured with

(parts

per

million).

include relativistic

including

an

the

18 22p2pj

accuracy of 20 ppm numbers one has to

experimental and quantum electrodynamics (QED) corrections, To

explain

terms of the second- and third-order in the fine-structure

require very high accuracy. In addition to the accurate reproduction of the energies, another motivation is that in the variational calculations, even though the energy is good, other physical observables might be less accurately determined. The increased accuracy of the energy, as we will demonstrate, eventually will lead to constant, which

very accurate values of other observables

as

well.

three-body general (m+M+m-)-type stability C A B system with unit charges has been thoroughly explored [861, and the like requirement for stability can be phrased as an empirical rule: In masses" ac[861. charges have to be borne by equal or nearly equal cordance with this prediction, systems such as H- (pe-e-), H2+ (ppe-), Ps-(e+e-e-), HD+(pde-), HT+(pte-), or tdg- are all bound, while (ppe-) or (pe+e-) are most probably not. Here p, p, d, and t are proton, antiproton, deuteron (2 H) and triton (3H) respectively. In the latter case, the particles with opposite charges form an atom, which does not bind the third particle. Some systems, e.g., the muonic molecules such as (ttft-) or (tdft-), remain bound even for L =-;,k 0 orbital angular domain of

The

a

"

,

momenta.

by

A second group of the Coulombic three-body problems is formed systems where not all the particles carry unit charges. The rep-

resentatives of this category are the helium atom (ae-e-) and the helium-like ions, where a stands for the 'He nucleus. These systems often form bound states with L atom

(ape-)

angular

has been observed

momentum states

We have

challenged

(L

our

=

=,4

0

as

[871 30

-

well. The

antiprotonic helium

and studied in very

bigh orbital

40) [88, 891.

method to calculate the

energies of

some

of these systems. In the calculations to be presented the number of basis functions superposed is mostly limited to be modest because our

primary

purpose is to demonstrate the overall

performance of the

cor-

related Gaussians and not to compete with well-established methods sharpened for these systems. We will increase the basis dimension to

8. Small atoms and molecules

152

reach

high

accuracy

only

in

cases

where such calculations

sidered to be important. The results of the calculations

are con-

axe

listed in

Table 8.1. Table 8.2 presents the parameters used in the calculations. The results are compared with those of other (mainly Hylleraas-type or

correlated

hyperspherical haxmonics basis)

calculations. Our results

reasonable agreement with other calculations. In most cases a basis size of K 200 was used in the SVM. The precision of the axe

in

=

results

be

improved by increasing the basis size as can be seen on the selected examples of Table 8.1. In these cases we reach almost the same precision as the other methods. The calculation extends to nonzero orbital angulax momentum states as well, including an e,,c 31 state of the antiprotonic helium atom or the a,mple for the L 3pe bound of the H- ion. These nonzero orbital angustates slightly can

=

lar momentum states the

as

well

as

L

=

0 states have been

investigated

by using global representation. The recovery of the results of other calculations (which are based on several different represenvector

tations of the orbital part of the

usefulness of the

wave

function)

convinces

us

of the

global vector representation. See Complement 8.4 for tdl-t molecule with the global vector

calculation of the

compaxative representation. a

To illustrate the convergence of the energy and the expectation values of average separation distances, the results at different basis sizes

are

tabulated in Table 8.3 for Ps-.

increasing the itself. One

Actually

accuracy is the conventional

can

the limit of further

precision of the computer

notice that at the basis size of K

100 the energy the first four figures of =

is accurate up to six decimal digits, but only the separation distances can be precisely determined.

the basis size, the virial coefficient falls below

high

accuracy of the calculation that all the

calculation

are

By increasing

10-'0, showing by the digits

of the reference

recovered.

Quite a few very accurate methods have been developed to solve the three-body Coulomb problem. It is very difficult to go beyond their precision. This is especially true for the methods which have been elaborated for a given system only, incorporating as much physical intuition as possible into the trial function or into the solution. In contrast with these methods, we use the same trial function, which is of Gaussian nature and therefore it is not tailored to Coulomb problems at all. Still, as the examples prove, one can get a sufficiently good solution in a unified and automatic way knowledge about the systems to cope with.

in

without

a

priori built-

The real power of the

8.2 Coulombic

three-body systems

153

Energies of different Coulombic three-body systems in atomic basis dhnension. See Table 8.2 for the constants which are the K is units. used in the calculations denoted superscripts a, b and c. Table 8.1.

System

State

K

SVM

Other method

K

Ref.

Ps-

Ise

600

-0.262005070226

-0.2620050702328

1488

COI-i-

600

-0.527710163

-0.527751016523

850

200

-0.1252865

-0.1252865

90

200

-112.97300a

-112.9730179a

200

-110.26210a

-110.2621165

a

ttA

Ise 3pe Ise 1PO

200

-105.98292

b

UIL

1D'

-105.982930b

2250

ttA

IF'

200

-101.43131'

-101.43'

200

MIL MIL td[t

IS'

200

-111.36444a

-111.364511474a

[691 [90] [911 [23] [231 [921 [931 [231 [20] [20] [941 [951 [681 [68] [681 [68] [68] [681 [681 [681 [681 [891 [96]

H-

UP

b

b

500 500

1400

IP,

200

-108.17923

1D'

200

-103.40849a

-103-408481a

1566

'He

Ise

600

-2.9037243769

-2.903724376984

700

He

Ise 3se

200

-2.9037242

-2.903724372437

100

He He He

He 'He

-108.179385

2662

200

-2.1752291

-2.175293782367

700

IP0 3po

200

-2.1238423

-2.123843086498

700

200

-2.1331635

-2.133164190779

700

1-D' 3D'

200

-2.0556201

-2.055620732852

700

700

-2.055338993068

-2.055338993337

700

IF' 3F'

200

-2.03125504

-2.031255144382

700

He

200

-2.03125506

-2.031255168403

700

He

IGe

200

-2.02000069058

-2.020000710898

700

He

3Ge

200

-2.02000069062

-2.020000710925

700

VHe+

L=31

300

-3.50760

-3.50763486

1728

'Li+

Ise

300

-7.279913

-7.279913

He

Table 8.2. The constants used in the calculations. The of the electron

mass.

energy in eV.

Set

a

masses are

m,,=7294.2618241, mp=1836.1515. R.

Set b

Set

c

Mt

5496.918

5496.92158

5496.918

Md

3670.481

3670.483014

3670.481

MI,

206.7686

206-768262

206.769

2R,,

27.2113961

27.2113961

27.2116

is the

in units

Rydberg

8. Small atoms and molecules

154

Energy and different separation distances for the (e+e-e-) three-body system as a function of the basis dimension K. The virial ratio 71 is defined by q 11 + (V)/(2(T))I. See Eq. (3.50). Atornic Table 8.3. Coulomble

=

units

are

-E

(,r2+_) (7-2

1 2

used. SVM

SVM

SVM

Hylleraas

(K=100)

(K=200)

(K=600)

[691

0.26200465

0.2620050648 0.262005070226 0.2620050702328

5.489

5.48962

5.489633252

5.489633252

8.548

8.54856

8.548580655

8.548580655

6.958

6.95832

6.95837

6.95837

9.65284

9.65291

9.65291

1

9.652

0.46

77

approach will

x

10-4

be

0.34

more

number of particles is most

as

The

or more

expedition

nium molecule

to

10-6

0.54

x

10-10

x

10-10

where the

than three and the method still works al-

while the other methods need tedious efforts.

particles

larger Coulombic systems

(PS2).

0.23

highlighted in the following sections, more

easily as before,

8.3 Four

x

starts with the

positro-

This exotic molecule consists of two electrons

and two

positrons. The possibility that the PS2 molecule or in general electron-positron system consisting of p positrons and q electrons form a bound system was originally suggested by Wheeler [97], and this question has been extensively studied since then. The existence of the positronium. negative ion Ps- (p 1, q 2) has experimentally been observed [981. The binding energy Of PS2 was first calculated by Hylleraas and Ore [991. To date, it has not been observed yet due to the dffficult experimental circum tances, and this fact has intensified the theoretical interest in solving- this Coulombic four-body problem [65, 100, 69, 101-1041. Actually the positron-electron annibil i n limits the

=

=

the lifetime of Ps2 to few nanoseconds. I-n

obtaining the

solution for the

PS2 molecule, it is useful to note PS2 is invariant with respect to the charge permutation, that is, the exchange of positive and negative charges. that the Hamiltonian for

The trial function should therefore either remain

unchanged or change

sign under the charge permutation operation. The ground PS2 turns out to be even under the charge permutation. its

state of

8.3 Four

or more

particles

155

The convergence of the energy Of PS2 against the increase of the basis dimension is shown in Table 8.4. The fact that the best vari-

ational calculation

[103]

in the correlated Gaussian basis is

already

at the basis size of 400 illustrates the power of the random

surpassed trials.

Table 8.4. The total energies (in a.u.) of the ground state and the bound excited-state of the PS2 molecule in atomic units. K is the basis dimension.

PS2

Method

(K (K SVM (K SVM (K SVM (K SVM (K CG [1031

SVM SVM

=

=

=

=

=

=

100) 200) 400) 800) 1200) 1600)

(L

0)

=

PS2

(L

=

1)

-0.516000069

-0-334376975

-0.516003119

-0.334405047

-0.516003666

-0.334407561

-0.516003778

-0.334408177

-0.5160037869

-0.334408234

-0-516003789058

-0-3344082658

-0-5160024 -0.51601+-0.00001

QMC [1041

possible existence of bound excited-states of the PS2 molecule [84, 85] by taldng all possible combinations of states with L 0, 1, 2 spins. By 0, 11 2,3 orbital angular momenta and S a bound excited state we mean such a state that cannot decay to any dissociation channels. The results of the calculation were negative in I (with negative parity) and all but one case. In the case of L of a second bound-state the existence S 0, the calculation predicts We have examined the

=

=

=

=

of the PS2 molecule. This unique bound-state has been found to be odd under the charge permutation operation. The convergence of the excited-state energy is shown in Table 8.4. Figure 8.1 summa izes the energy spectra of the bound states made up of two positrons and two electrons

together with the

relevant thresholds.

One may ask the question of why the second bound-state cannot decay to two Ps atoms in spite of the fact that it is located above the threshold of Ps (1S) +Ps(IS). Since the total spin of the state is to zero, it

that

they

dissociate into two Ps

can

have

equal spins

(ground state)

and the relative orbital

atoms

coupled provided

angular momentum

1. (Recall that the Hamiltonian preserves spin, between them is L orbital angular momentum and parity.) However, this is apparently =

impossible

equal spins are bosons and their L. Consequently, the PS2 molecule

because two Ps atoms of

relative motion

can

only have

even

156

8. Small atoms and molecules

0

Ps(2P)+e++e-0.1

-0.2

-

Ps(lS)+e++e-'

Ps-+e+

Cd -0.3

IP0

-

Ps(IS)+Ps(2P)

>1 0)

-0.4

-

W

-0.5

-Ps(IS)+PS(IS)

-0.6

Se

PS2

-0.7

Fig. 8.1. The energy spectrum are given in atomic units.

with L

=

I and

of electron and positron systems.

Energies

negative paxity cannot decay into the ground states of

two Ps

atoms, that is, the lowest threshold of Ps(IS)+Ps(IS). Since the energy of this L 1 state is calculated to be E -0-3344 a.u. (see =

Table

=

8.4), (-0.3125 au.) of Ps(IS) + Ps(2P), this state is stable against autodissociation into this which is lower than the next threshold

channel. The

binding energy of this state is 0.5961 e-V from this second threshold, about 40% more tightly bound than that of the ground state Of PS2 whose binding energy is 0.4355 eV from the lowest threshold. are

The expectation values of vaxious listed in Table 8.5. In the

quantities for the PS2 molecule

PS2 molecule we deal with antiparticles, so the electronpositron pair can annihilate. The second bound-state may decay either by annihilation or by an electric dipole transition to the ground state [851. The most dominant annihilation is accompanied by the emission of two photons with energy of about 0.5 MeV each. To have an estimate for the decay width due to the annihilation we have substituted

8.3 Four

or more

particles

157

Properties of the ground and excited states of the PS2 molecule. positrons; are labelled I and 3 and the electrons are 2 and 4. Because (r14) of charge permutation symmetry, some equalities hold, e.g. (r12) Table 8.5. The

=

(r32)

=

(r,34).

Atomic units

PS2

(L

are

used.

0)

=

PS2

(L

=

1)

(r12) (r13)

4.4871530

7.56881891

6.0332070

8.8575844

(r212

29.112633

80.173836

46.374735

96.085514

2

r13 3

( r12) 3 (r 13 )

253.04611

1041.3251

443.85244

1226.7955

(412)

2807.2718

15612.112

4 13

5202.0371

17939-574

(r 21) (r.3' -2) r12 -2) r13

0.36839693

0.24082648

0.22079007

0.147244820

0.30310361

0.16081514

0.073444303

0.032230158

(1'12'TI3) ('r12 'T14) (5(rl2)) (5(rl3))

23.187368

48.042757

(r ) 12

5.9252651

32.131079

0.0221151

0.0112091

0.0006259

0.00014591

(V2) 1

-0.258001894

-0.16720401

(V1 V2)

0.1307732538

0.091656853

(VI'V3) 11 + (V) /(2(T))

-0.0035446132

-0-016109693

*

the

0.3

10-9

x

probability density

(J(r12))

,

of

into the formula

rannihi

=

47

x

10-6

electron at the

position of

a

positron,

[1021

(MC622 ) 2hc(TIjJ(rj-T2)jTf) 62

=

an

0.36

4ir-(hc)

4

hcaOI(5(rI2))i

(8.2)

equal to J0 (Tf 15(rl r2) ITf) with ao Roughly speaking, the Metime is inversely probeing portional to the probability. The Metime due to the annihilation is estimated to be 0.44 ns. This is twice that of the ground state (0.22

where

(,S(r12)), given

in a.u., is

-

the Bohr radius.

ns). dipole transition from the excited state emits one photon with energy of 4.94 eV. The decay width Idjp&,, for this transition The electric

8. Small atoms and molecules

158

is calculated

through the reduced transition probability B(EI) dipole operator D.:

electric

16v

Tdipole

':--

(E) 3B(EI;

I-

0+),

-->-

he

9

for tile

(8-3)

where I

B(EI; 1-

--+

0+)

=

)7 I (Oind I DI, ,

_

M) 12

(8.4)

1

with 4

qi 1ri

Djz

X4

-

I Ylp (ri

-

X4)

IIIere X4 is the center-of-mass of the

(4.94 eV)

tation energy

B(El)

dipole

P-92 molecule and E is the exci-

of the second bound-state. We calculated the

value and obtained

electric

(8-5)

-

B(EI)

=

0.87e2a 2. The lifetime due 0

transition has been found to be 2.1

ns.

The

to the

branching

dipole transition is thus about 17 % of the total decay rate. Therefore, both branches contribute to the decay of the excited state of the PS2 molecule. Its lifetime is finally estimated to be about of the electric

The excitation energy of 4.94 eV found for PS2 is different by 0.16 eV from the corresponding excitation energy (5.10 eV) of a Ps 0.37

ns.

atom. This difference

to be

large enough to detect its existence, e.g. in the photon absorption spectrum of the positronium gas. Before discussing the spatial distribution of the PS2 molecule, let us recall that the average distance (r+-) between the positron and the electron is 3 a.u. in the ground state of the Ps atom, while it is 10

a.u.

first excited state. The root-mean-square radius

in its

(ri

-

X'j

)2),

culated to be 3.61

surprising a

system of

of the

a.u.

5.66 a.u., 1.5 times

if

seems

larger

one assumes a

ground

The

rms

PS2 molecule

is cal-

radius of the second bound-state is

than that of the

ground

state. This is not

that the second bound-state is

Ps atom in its

(spatially extended)

state of the

(rms),

ground

state and

a

excited state. To check the

essentially

Ps atom in its first

validity

of this

as-

sumption, we have restricted the model space to include only this type of configurations. This can be achieved by a special choice of the uki parameters of that is, the

Eq. (8-1). The energy converged to -0.323 a.u., Ps(1S) +Ps(2P) system with zero relative orbital angular

momentum forms state of the

a

bound state with energy close to that of L

PS2 molecule, therefore this configuration

is

lik-ely

=

to

1

be

8.3 Four

the dominant

configuration in this molecule.

uration, the Ps- + e+

or

Ps+ + e- with L

=

or more

There is

particles

159

second

config-

a

I relative orbital

motion,

intuitively may look important because two oppositely charged particles attract each other, but it is barely bound (E -0.315 a.u).

which

=

1 state The average distances in Table 8.5 show that in the L the two atoms are well separated. In fact we can estimate the root=

mean-square distance d between the two atoms

by

2

d2

I'l +7'2

7'3 +7'4

2

2

(2(r12 ) 2

4

(,r213)

+

-

) (8-6)

2(rl2*rl4)

The symmetry properties of the PS2 wave function are used to obtain 6.93 a.u. the second equality. Using the values of Table 8.5 yields d =

for the L

=

I excited state and d

state. One cannot

give

a

direct

Arij

The correlation function defined

gives

(TfIJ(ri

=

more

-

-

(r,2

of the

(,rj)2

ground ground or

is

0

laxge.

by

(8.7) on a

system than just various average

quantity can be calculated for the correlated Gaussians

by using Eq. (A.30) =

=

=

r) ITf)

detailed information

distances. This

Tf with L

rj

for the L

a.u.

geometrical picture

excited state because the variance

C(r)

4.82

=

or

(A.136).

0, C(r) becomes

monopole density.

a

ground-state wave function of only r, which is called the

For the

function

For the excited-state

wave

function with L

=

1,

monopole and quadrupole densities. and the electron-positron electron-electron the 8.2 displays Figure correlation functions r 2C(r) for the ground-state of the PS2 molecule. The peak position of the electron-electron correlation function is shifted to a larger distance than that of the electron-positron correla-

C(r)

consists of the two terms of

tion function. The latter has much broader distribution and reaches

farther in distances

compared

to the

corresponding function

of

a

Ps

atom.

Figure

8.3

displays

the electron-electron and

electron-positron

cor-

relation functions for the second bowid-state of the PS2 molecule. As I state consists above, the correlation function for the L of the monopole and quadrupole densities and their shapes depend on the magnetic quantum number M of the wave function. Of course the M-dependence of the shapes is not independent of each other

mentioned

=

8. Small atoms and molecules

160

0.020

0.015

Cd 0.010

0.005

0.000 0

Fig.

4

8.2. The correlation functions

molecule. The solid dashed

the

2

curve

r

6

8

r

(a.u.)

2C(r)

for the

12

ground

14

state of the

PS2

denotes the electron-electron correlation and the the electron-positron correlation. For the sake of comparison, curve

electron-positron correlation function for

dotted

10

a

Ps atom is drawn

by

the

curve.

but is related

by the Clebsch-Gordan coefficient. See Eq. (A.136). quadrupole density is contributed from only the P wave of the electron-positron relative motion, while the monopole density is contributed by both S and P waves. Figure 8.3 plots the correlation funcThe

tions for both

(a)

M

=

0 and

(b)

M

=

1. As the correlation function

axiaUy symmetric around the z axis and has a reflection symmetry with respect to the xy plane, the correlation function sliced on the xz plane is drawn as a function of x (x > 0), z (z > 0). The electronelectron correlation function has a peak at the point corresponding to the average distance of 7.57 a.u. The electron-positron correlation function has two peaks reflecting the fact that the basic structure of the second bound-state is a weakly coupled system of a Ps atom in the L 0 state and another Ps atom in the L 1 spatially extended state. The peak located at a larger distance from the origin is due to the P-wave component of the PS2 molecule. The hydrogen and positronium molecules can be considered as members of the same family as both are quantum-mechanical fermio-nic is

=

=

four-body systems of two positively and two negatively charged identical particles. But they are at the opposite ends of the (M+M+m-m-)-

8.3 Four

x

x

(a.u.)

(a.u.)

x

z

(a.u.)

z

(a.u.)

0 x

or more

(a.u.)

161

particles

z

(a.u.) z

(a.u.)

(a.u.)

Fig. 8.3. The correlation fimctions rC(r) in atomic units, raultiplied by one thousand, for the second bound-state of the PS2 molecule. The z comI for 0 for (a) and M ponent of the orbital angular momentum is M (b). Drawn on the xz plane are the corresponding contour maps. =

=

8. Small atoms and molecules

162

type Coulombic systems called biexcitons biexciton and two

(or

biexciton

holes,

molecule),

is observed in

a

a

or

bound

variety

excitonic molecules. The

complex of

two electrons

of semiconductors

[105, 106].

See also Sect. 10.1. The biexciton molecule is characterized mass

ratio

o-

=

m/M. Apart

by the connection, however, their

from this

properties are radically different, e.g., H2 is an adiabatic but PS2 is a highly nonadiabatic system. Moreover, while in the case of the H2 molecule many bound excited-states have been observed experimentally and later studied theoretically, in the case of the PS2 molecule only the ground state and the unique excited state discussed above have so far been predicted theoretically. See also Complement 8.3 for the stability of the biexciton molecule. Figure 8.4 displays the dependence of the binding energy of the biexciton molecule on the mass ratio a m/M. The changes of the binding energies in the ground state (L 0) and the excited statues with L 1 and negative parity is si-milar. Both the ground and excited states become less bound by changing the mass ratio from H2 to PS21 though the binding of the excited state decreases to a somewhat lesser =

=

=

extent. The energy of the transition from the excited state to the

ground state is also shown in this figure. This transition may take place in an external field, for example. By increasing the mass M of the positively charged paxticles tbowa,rd infinity, one arrives at the energy of the C I H,, 2p-x state of the H2 molecule. This state is formed by an excited H-atom and a groundstate HI-atom. Consequently, a statement similar to the case of the PS2 molecule is valid for the biexcitonic molecule: The second bound-state of the biexciton molecule is of

a

ground-state

dominantly formed by

exciton and

an

L

=

an

interacting

pair

1 excited-state exciton.

The rule that the Pauli

principle forbids odd partial waves between identical bosons also applies to the biexciton with L I and negative The second bound-state of the biexciton molecule cannot decay parity. to two ground-state excitons. A somewhat similar situation exists in the 3p, state of the H- ion as well, where its second bound state cannot decay due to the parity conservation. By changing the mass ratio in that (M+m-m-) system, however, this kind of state disappears for oI and the Ps- ion is known to have only one bound state. =

=

Tables 8.6-8.8 show tem

our

results for various other Coulombic sys-

.

The tivated

investigation of the stability of positronic atoms has been nioby the use of positrons as a tool for spectroscopy (positron

8.3 Four

or more

163

particles

0.15

0.10 CU

0.05

0.00 0.0

0.4

0.2

0.6

0.8

to

M/M

Fig.

8.4. The

mass

ratio

o-

binding

=

m/M.

state, and the solid

energy of the biexciton molecule as a function of the curve is the binding energy of the ground

The dotted

curve

is that of the first excited state with L

Table 8.6.

curve

Energies of different Coulombic four-body systems

I and

=

is the energy difference, multiplied negative parity third, between the first excited state and the ground state.

The dashed

by one

in atomic

units. K is the basis dimension.

System

State

K

SVM

Other method

K

Ref.

PS2

Ise IP0

800

-0-516003778

-0.516002

400

[102] [107] [1071 [1071 [1031

800

-0.334408112

600

-7.478058

-7.47806032

1589

Li

Ise 1PO

1000

-7.410151

-7.410156521

1715

Li

'D'

1000

-7-335520

-7.335523540

1673

'HPS

Ise

1200

-0.7891964

-0.7891794

PS2 Li

8. Small atoms and molecules

164

Table 8.7.

Energies of different Coulombic five-body systems

in atomic

units. K is the basis dimension. The Li- energy with K = oo is the extrapolated one [1091, where E = -7.500577 is given by multiconfiguration

Hartree-Fock calculations with K

=

2997.

System

State

K

SVM

Other method

K

Ref.

Be

Ise Ise

500

-14.6673

-14.667355

1200

600

-7-50012

-7-50076

00

[1081 [1091

Li-

Ise Ise

(27r+, 3,-1-) Li +

e+

Table 8.8.

Energies

200

-0-5493

1000

-7.53218

of different Coulombic

six-body systems

in atomic

units. K is the basis dimension.

System

State

K

SVM

(37,-+,37r-)

IS' Ise Ise

300

-0.820

600

-7.73855

1000

-14.692

Li + Ps

Be+e+

annihilation

spectroscopy) is whether

in condensed matter

physics.

An

intrigu-

or a chemically stable system containing a ing question positron or a positronium could be formed in the various targets. This

not

be answered

only by a sophisticated calculation or experiment because the mechanism responsible for binding the positron to the neutral atom is the polarization potential present in the atom+e+ system. The boundness of the hydrogen positride (positronium hydride) HPs was predicted theoretically by Ore [99] in 1951 and it has recently been created and observed in collisions between positrons and methane [1101. The properties of HPs is discussed in [851. The use of the SVM proved for the first time that the positronic lithium (Li+e-r [1111 and the positronic beryllium (Be+e+) [1121 are stable. We see from the tables that the positron separation energy of the positronic lithbun is 0.054 a.u. Below the Li+e+ channel the Li++Ps channel is question

can

open and the

energy of the

positronic lithium is only 0.0022 a.u. against the dissociation into the Li++Ps channel. A calculation has to be accurate at least to 10-3 a.u. to answer the stability of the

binding

positronic litbium. Likewise, the positron separation energy of the

Be+e+ system

typically

is

only

about 0.01

0.025

a.u.

a.u.

one

Due to the

tiny binding energies of

has to. be able to reach

high

accuracy

8.4 Small molecules

165

6-particle systems. A naive picture of these systems is that the positron orbiting around the neutral atom slightly polarizes the negative electron cloud, and the positron is bound by the resulting in these

attraction.

(as a fall N-body solution) for the investigation of the stability of much larger systems (e.g. Sodium plus positron) To extend the method

question. One can, however, try to use a "frozen core approximation?'. In this approximation the positively charged core is considered to be passive (its polarization is neglected) and the problem is is out of

model space where the single-paxticle orbitals are orthogonal to the core orbitals. One has to solve the modified Schr6dinger

solved in

a

equation of the form

(H + AP)Tf

=

with

ETI-

P

(8-8)

Oi) (Oi iGoccupied

produces wave functions that are orthogonal to the core orbitals provided the positive constant A is large enough. The projection operator P is an example for the nonlocal potentials discussed in Sect. 7.5. See also Complement 11.4. One can validate this approximation by comparing it to the "exact" fuU N-body calculation for Li+e+. This approximation turns out to be very accurate, reproducing the first six digits of the result of the full calculation [1121. Assuming that the accuracy holds for larger systems, one seems to find the stability of positronic sodium (Na+e+) [1121. which

8.4 Small molecules As it case

was

mentioned at the

demands

a

special

beginning

of this

assumed to take combinations of the form 1

g(s; A, x) where

Aij

and

functions. The x.

exp

=

Note that

s

(_2

=

is

a

Mx +

f8li S21

"generator x

chapter, the molecular

treatment. The variational trial function is

-7

(6.19)

9x),

SN-11

coordinates"

(8.9) are s

parameters of the basis

are

chosen

conforming

to

set of relative coordinates. Our aim here is

to calculate the energy of the

system which

can

be

directly

com-

pared to experiment without recourse to the adiabatic treatment like the Born-Oppenheimer approximation. Each basis function includes !V(IV 1) /2 + 3 (IV 1) parameters to be optimized. These parameters -

-

8. Small atoms and molecules

166

describe various correlations. The matrix A describes the electronic

correlations and motions, while the generator coordinate s makes the function flexible and allows us to represent several "peaks" of

wave

the

distribution

density

the holes

when, for example

in the

well separated and the electrons them. around 0 the function By choosing s are

=

hydrogenic limit, "atomic orbits"

axe on

(8.9)

at the

'has its

maxhnum

origin and this limit is suitable around a1, when m/M the paxticles with nearly equal masses are moving equally fast. At the hydrogenic limit, when the motion of the heavy particles are very slow compared to the light ones, the density distribution has several peaks =

=

axound the attractive centers, and to represent these configurations need to shift the maximum of the trial functions out of the origin

we

by choosings appropriately. The usefulness of the generator coordinates in the basis function (8.6) can be understood by the following example. Let us try to calculate the energy of the IH+ this basis with and without 2 by using (that is by setting them to zero) the generator coordinates. The latter

form

corresponds

to the correlated Gaussians for L

of that system is -0.6026

basis of K

=

a.u..

300 Gaussians

0. The energy Without the generator coordinates a

give

-0.5999

a.u.

=

for this molecule. The

inclusion of the generator coordinate immediately h-nproves the con10 basis states vergence and one can get -0.6024 a.u. by using K =

only! Table 8.9 shows ions

consisting

examples

of calculations for the molecules and the

of protons and electrons..

Table 8.9. Ground state

energies of small molecules

in atomic units. K is

the basis dimension.

System

K

"OH+ 2 0OH2 "OH+ 3

SVM

Other method

K

Ref.

50

-0.602634429

-0.602634214

160

100

-1-17445

-1-174475714

1200

100

-1.34351

-1.343835624

600

[1131 [1131 [1141

167

Complements 8.1 The cusp condition for the Coulomb potential It is desirable that the trial function satisfies the proper asymptotic behavior or the special boundary condition as demanded by a given

special boundary condition, the cusp condition [115] known for the Coulomb potential, by using the hydrogen atom as an example. The local energy for the hydrogen atom is given by Hamiltonian. We discuss

h2 1

Ej"'c

a

192 Tf

-

-r-2

2m Tf

where hl is the

angular

h2

2 (9Tf + r

-5r- )

momentum

1

e2

2

(8-10)

1 IIf

+

.M r2 Tf

r

operator. As

was

discussed in

Sect. 3.2, the local energy for the exact wave function turns out to be a constant. The Coulomb potential in the local energy gives a singular 0. For the local energy to be a constant, this singular behavior at r =

behavior must be

for

compensated

by

the kinetic energy term. For

an S wave, where the wave function Tf has no angular dependence, 12Tf 0 and the constancy of El.,r requires that the second term in =

the bracket in

Eq. (8.10) cancel

the

singular

behavior of the Coulomb

potential: I

2

aTf)

Tf 9r

-me h2

r=o

ao

where ao is the Bohr radius. It is easy to see that an exponenexp(-r/a) for the radial part of the ground-state wave

tial form of

function leads to sen

a

constant local

density

if and

only

if

to be ao. The constant of the local energy is then

-0/(2ma2) drogen

=

_Me4/(2h2)

=

-El

as

expected,

atom ionization energy without the

a

is cho-

equal

where E, is the

to

hy-

proton recoil effect, that

is, the well-known energy of 13.6 eV.

angular dependence, it has to take care I/r singularities. Then Tf may be expressed I/r as a product of radial and angular parts: Tf r'R(r)Y(S?), where s 0. is a positive constant and R(r) is assumed to be nonzero at r Substituting Tf into Eq. (8.10), we obtain For

a

general

case

when Tf has 2

and

of both the

=

=

h?

Eloc 2m

+

1

a2 R

( R -5r-2

h2 1 2 __1 Y 2Tar2 Y

2(s + 1)

8(8+1)

1 M

+

+ r

R 9r

r2

2 -

_.

r

(8-12)

Complements

168

As R does not vanish at

r

0, 1IR gives

=

origin. The condition that the local following result: 1

I

( OR) 9r R

We know that the second

12y equation

no

singularity

at the

energy is constant leads to the

=

(s + 1)ao'

=o

rise to

(8.13)

S(S + 1)y

is satisfied if and

only

if

s

is

a

positive integer 1, and then the first equation determines the correct behavior of R near the origin as R(r) oc exp(-r/(l + I)ao). Equations known to be the cusp conditions. Let us attempt to solve the S-wave hydrogen atom variationally with Gaussian basis functions, exp[-(a/2)(r/a0)2J' where a is a vari-

(8.11)

and

(8.13)

are

ational parameter. We functions that lead to

use a

Gaussians

as

an

example of such basis

rather accurate solution but

are

poor in

satisfying the cusp condition. When a single basis function is used, the optimal value of a is 16/(9z), giving the minimum energy of -8/(37t-)EI -0.849EI. A combination of a few terms approximates the ground-state energy quite well. The parameter values of a are determined by the SVM. Table 8.10 shows sample results of such calculations obtained with the code given in [81]. The calculation with five Gaussians already reproduces the energy up to three digits. The wave function obtained with ten Gaussians can reproduce both the energy and the mean values of r and I/r fairly accurately. The over=

lap of the wave function with the exact wave function is very close to unity. We may conclude that the Gaussian basis can predict physical quantities to high accuracy. Of course, the solution does not satisfy the proper asymptotic behavior at large distances and, moreover, always gives zero for the cusp value of Eq. (8.11). The local energy displayed in Fig. 8.5 for the variational wave function indicates that with increasing K it tends to show smaller and smaller deviations from the exact wave function except for the singular points mentioned above. The local energy at large r deviates from the correct value because the Gaussian basis has the wrong asymptotic behavior. It is possible to generalize the above arguments for the cusp value in a system of particles interacting via Coulomb potentials. Evaluating the cusp value for a pair of particles with charges qj and qj, we obtain

(If 16(ri

-

2'j) alriarj I Of)

(T/IJ(ri

-

rj)ITI')

I-tijqiqj h2

(8-14)

where tzij is the reduced mass of the two particles. The left-hand side of Eq. (8.14) is expressed with the matrix elements involving

C8.2 The chemical bond: The H+ ion 2

J(r)

=

J(r)/(47rr2)

used to test the

The cusp values for a pair of paxticles quality of the variational solution at the .

are

169

often

particles'

coalescence.

Table 8.10. Variational solution for the

hydrogen

of Gaussian basis functions. The last

shows the exact values. Ei is the is the Bohr radius.

hydrogen K

atom ionization energy and ao

E

E,

((_L_)-2) ao

atom with

a

number K

row

ao

((_E_)2) ao

ao

Overlap

1

-0.8488264

1.131774

0.8488284

1.499996

2.650706

0.9568351

3

-0.9939585

1.903352

0.9939409

1.491519

2.922759

0.9987560

5

-0.9996191

1.986219

0.9995692

1.499147

2.991284

0.9999446

10

-0.9999998

1.999700

0.9999958

1.500004

3.000014

0.9999999

-1

2

1

1.5

3

1

K= 1

0-, IN.

-4-

K=3

K=10

1 %

0

5

10

15

20

rlao Fig. 8.5. hydrogen

The local energy

curve

plotted for the variational solution

of the

atom. K denotes the number of Gaussian basis functions.

8.2 The chemical bond. The

H+ 2

ion

Quantum mechanics enables us to understand the chemical bond, which is responsible for the formation of molecules from isolated atoms. The chemical bonding phenomenon involves the delocalization of electrons in an atom to gain attraction from the other nuclei when

Complements

170

the atoms

close to each other. We take up the simplest possiH2+ ion, to understand what an important role the

come

ble molecule, the

Hellmann-Feynman

and virial theorems

[1]

of the chemical bond. See

play for clarifying the origin

for detail.

ffilly quantuin-mechanical description of a molecule is a complex problem. This problem is usually simplified by using the BornOppenheimer approximation, where the electronic motion is separated from the nuclear motion, considering the fact that the electron mass is much smaller than that of the nuclei. One starts with determining the motion of the electrons for a fixed configuration R of the nuclei and The

ground state, of energy U(R), of the electronic system. Then one assumes that,when R varies, the electronic system always remains in the ground state corresponding to R, that is the electrons follow adiabatically the motion of the nuclei. The chemical bond is then determined by studying the nuclear motion in a potential energy V(R) which comprises the Coulomb repulsion between the nuclei and obtains the

U(R)Ht 2

Let R be the distance vector between the two protons of the ion and

v

be the

vector of the electron with

position

respect

to the

center-of-mass of the protons. The electron motion is determined the Hamiltonian

2[t

Note that R is

equal

is

the

m

to

e2

e2

p2

H,e( R)

IT

just

a

-

by

stage. The reduced mass jL where M is the mass of the proton and

parameter

2Mm/(2M + m),

(8-15)

IT + RI 2

Al 2

at this

of the electron. The electronic energy U(R) is the lowest of the Hamiltonian (8.15). It is clear that U(R) becomes

mass

eigenvalue

only. The Schr8dinger equation for the Hamiltonian completely separated in elliptical coordinates with respect (8.15) to the foci, R/2 and -R/2. We do not need its exact solution in the following discussion, but note that it is well approximated by the variational calculation using a trial function of the form a

function of R is

Tf

-01"

where at

s.

(Z' R) +'OL' (Z' R),

01, (Z, s) is the charge Z is

The

(8.16)

_

2

2

ls a

hydrogenic orbital

of radius

variational parameter and its

ao/Z

centered

optimal

value

is deternUned to miniraize the energy for each R. The optimal value 1 for R ---* co. At 0 to Z 2 for R of Z decreases froin Z --+

cc

the system will switch

=

=

=

R

over

to

a

configuration

of the

hydrogen

C8.3

atom and the

Stability

proton. Between these

of

hydrogen-like

molecules

extremes, Z is

two

function of R. The energy U(R) is -4E, (2M/(2M + and approaches -E, (MI (M + m)) for R oo.

a

m))

171

decreasing for R

=

0

By using the virial theorem (3-49) and Eq. (3.56) with A R, Ry7 R, we can show that the expectation values, (T) and (W), of the kinetic energy and potential energy of H,..(R) satisfy the relation d

2(T)

+

(W)

+R

dR

U(R)

=

(8.17)

0. '9

Here we have used the fact that WA+R. aR W R d dR to

=

-W and

Rr-aR -U(R)

U(R), enables us equation, together with (T) + (W) U(R). the protons, between of the potential express (T) and (W in terms This

V(R)

=

U(R)

+

=

(e 2IR),

as

follows:

d

d

(T)

=

-U(R)

-

R

dR

U(R)

=

U(R)

=

-V(R)

-

R dR

=

2U(R)

+R

dR

For the chemical bond to must have

(T)

,

clude from

occur

2V(R)

in the

+R

dR

V(R)

-(8.18)

-

R

H+2

system, the potential V(R) --+ oc) -Er at some point

V(R V(Ro:) < -E-r have to be met. Since oc (see Eq. (3.53)), we can con-2E, at R at equilibrium (R Eq. (8.18) that, RO), the electronic

a

deeper

minimum

that is, V(Ro) Er and (W)

Ro,

e2

d

d

(W)

V(R),

=

than

-

0 and

-- -

-

=

kinetic energy is increased and the electronic potential energy is decreased. The lowering of the electronic potential energy is large enough to cancel the

repulsion

for the chemical bond.

and

V(Ro)

-

V(R

-+

between the protons, and that is

According to

oo)

=

an

exact

responsible 2.00ao calculation, Ro -

-2.79 eV.

challenging to perform a nonadiabatic calculation in which no separation of the electron and nuclear motion is made. The validity of the Born-Oppenheimer approximation can be tested in such a calculation. Furthermore, the development of the nonadiabatic treatment for a smaU molecule is of importance in its own right because the adiabaticity may be questionable when the electron is replaced with heavier particles like the muon or the pion. The excellent results obIt is

tained in Sects. 8.2-8.4 indicate that realistic nonadiabatic, calculations are

in fact

possible

in the correlated Gaussian basis.

172

8.3

Complements molecules

Stability of hydrogen-like

The existence of bound states of systems composed of particles with unit charge attracts considerable attention. We discuss this problem here

by applying

of the

some

principles discussed

in

Chap. 3. always bound

The system of the hydrogen-like atom, (M+m-), is and its binding energy is equal to jL/2 in units of e

1, where p stability of a

Mm/(M+m)

=

is the reduced

-mass.

=

I and h

=

What about the

hydrogen-like molecule (M+M+m-m-)? This system is characterized by the mass ratio om/M. Two well-known examples include the hydrogen molecule (a < 1) and the positronium molecule PS2 (o1). Another example is the biexciton molecule [105, 1061. See =

=

Sect. 8.3. The value of 0 <

Emits,

< I.

c-

o-

of the biexcitons

A molecule is bound

can

vary between the two

provided that

the threshold

of any dissociation channel is higher than the lowest energy of the system. The lowest dissociation channel is (M+m-) + (M+m-) for this system, and its threshold energy is Eth the hydrogen-like molecule has been studied

(see Fig. 8.4). However,

-ft. The

stability of

numerically

in Sect. 8.3

=

theoretical argument [1011 makes it possible to prove that the system is bound for arbitrary values of o-, that is, the ground-state energy E of the system is lower than Eth. The proof relies

on

stability

the

a

scaling property of the Coulombic Hamiltonian and the point of the proof given in [101] will be

Of PS2. The basic

shown below. The Hamiltonian of the system -ff

=

-ffS

+

1

_as

=

4[t +

(P21 +P22+P32 +P42)

(

2 e

1

1 +

the

mass

nothing

I -

r34

7'12

1

4-M

is

4m

1 -

r13

) ( 2+ Pi

r14

-

T'24

r23

),

a

-+

=

A H(PS2), M,

(8.20)

2

P44:) P22_P2_ 3

but the Hamiltonian of

mX of

I

I -

a

(8.21)

-

system

(X+X+X-X-)

particle X being equal to 2p. By applying transformation ri Ari (,X m,/(21L)), we obtain I-Is

as

(8-19)

-

HS

is written

HA,

I

HA

(M+M+m-m-)

a

with

scaling

=

(8.22)

C8.3

where the

m,.

is the electron

Stability and

mass

molecule. This

positronium HS, ES,

state energy of

by Es

=

(2A/Tne)E(PS2).

from the the

can

of

hydrogen-like molecules

H(PS2)

is the Hamiltonian for

indicates that the

equation

be obtained from that Of

Note that this relation

groundPS2, E(PS2),

also be obtained

can

Helh-nann-Feynman theorem and the virial theorem. In fact Eqs. (3.38) and (3.53) enables one to obtain (mx 2/-t)

of

use

173

=

d

a

ES

=

dTax

1

( fisjTax-Hsjfis)

=

-- !PSjTSjPS) Tax

I

(8.23)

ES,

-

Tax

which leads to the solution that is the

(Ps

ground-state

wave

E,,/mx

independent of mX. Here function of HS and TS is the kinetic is

energy of HS.

According to the Ritz theorem following relation

the

ground-state

energy

El of H

satisfies the

El :! ((fiS IHS + HA PS)

(8.24)

-

The term

HA is odd under the interchange P of the masses M and -HAP. Then by using that (PS is invariant under i.e., PHA

m,

=

(0SjpHApj(pS) _((pSjHAp2j0S) ((PsIHA10s) The side of 0. Eq. (8.24) is thus equal right-hand -(0sjHAj(Ps) to ((fisjHsj0s) ES, and we obtain P

we

have

El

-

=

Eth :! ES

-

(-A)

=

2A =

M,

(E(PS2)

-

(-

=

M.

2

))

(8.25)

-

The energy of -m,/2 is the threshold for P,92 to decay into two Ps atoms. If the stability Of PS2 is established, that is, E(PS2) +

(m,/2)

0, then

<

we can

the

hydrogen-like

[991

calculated the energy

showed its

immediately from Eq. (8.25) that always stable. In fact Hylleraas and Ore Of PS2 by using a simple trial function and

conclude

molecule is

stability.

It is of interest to examine the

stability of a hydrogen-antihydrogen

like molecular system, (M+m+M-m-) [1041. The lowest threshold of this system is now Eth -(M/4) (m/4) corresponding to the dis-

sociation

(M+M-)

+

(m+m-)

and gets

deeper

and

deeper

as

M in-

creases, which is in contrast to the case of the hydrogen-like molecule. It is un I ikely that the hydrogen-antihydrogen system gets lower energy

Complements

174

than the threshold. It is thus

expected

that there is

a

critical

mass ra

M/m beyond which the system becomes unstable. According to the calculations hn [104, 1161, the stability limit is M/m < 2.1.

tio,

Application of global vectors to muonic molecules The aim of this Complement is to show the utility of the global vector v of Eq. (6.4) for describing the angular part of the variational trial function. As a test example we take up a Coulombic, three-body system, the tdIL molecule, which has attracted much attention in relation to muon catalyzed fusion [1171. The excited P state especially plays a key role in the fusion since it lies close to the threshold for the decay 8.4

to the

ttt

atom and the deuteron.

The basis function

we use

is

fKLM of Eq. (6.27).

matrix elements for this function

Chap.

7 and the

appendix.

can

be calculated with the method of

Without loss of

parameters ul and U2 which define U +U22 1. Each basis function for =

The Hamiltonian

v

generality

can

be normalized to

given

a

the variational

satisfy

set of KLM values thus

contains at most four nonlinear parameters, three of which

come

from

positive-definite to assure the 6DG, general be expressed as A

the matrix A. The matrix A has to be finite

where G is one

Of

norm

a

fKLM,

2x2

and

can

in

=

orthogonal matrix

(

cosO

-sinO

sin,& cos

?

specified by just

parameter V and D is a diagonal matrix including positive d, and d2 values.

two

diagonal

elements of

The accuracy of the variational solution depends on how the parameters ul, V, di, and d2 are given [331. The most naive choice would

be to take G

ing only

a

as a

single

unit matrix

(6

=

0)

,

which is

equivalent

set of relative coordinates x, and then to

to

us-

try

to

im-

by including successively higher partial appropriate choice of K and ul values. Many examples show [20, 29, 30, 311, however, that this type of single-channel calculation does not work well, especially in the case where the adiabatic approximation is questionable as in the present example. Gx correspond to other The matrix G may be chosen to let y particular coordinate sets such as the so-called rearrangement cha n nel [201. (For Gx to correspond to the rearrangement channel, the length scales of x and y in general have to be modified appropriately.) Three possible rearrangement channels expressed in the Jacobi reach convergence

plied by

waves

an

=

particles d, t, and tL are labelled particle 1, 2, and 3, the three patterns in Fig. 2.2 correspond to (tlL)d, (/-td)t, (dt)IL arrangements, respectively. If x is understood coordinate set

are

drawn in

Fig.

2.2. If the

C8.4

Application

of

global

vectors to muonic molecules

175

to stand for the coordinate set of the

(tl-t)d arrangement,

ordinate set

arrangement is obtained

to the other

the

co-

corresponding by choosing such an appropriate,& value that is uniquely determined by the change of the coordinates. With this choice of ?Y, we can write ,'N DGx i Ax dj y', + d2y22 Dy The following three simple types of bases were chosen: =

=

=

*

(i)

K

0 and A

=

dDG,

=

trices

connecting only explained above.

K

(ii) (iii)

=

K

0

or

1 and the choice of A is the

0 and A

=

where G is restricted to the

=

special

ma-

the three sets of rearrangement channels

dDG,

where G is

same as

now an

in

case

as

(i).

arbitrary orthogonal

matrix.

As

mentioned in Sect. 6.2, the angular part with K 0 describes only the stretched configuration, 11 + 12 L, and therefore was

=

-

the basis of type (i) allows rather limited angular correlations between the particles. In fact, the possible (Ili 12) values are given by

(1, L

-

1), (1

=

0,

...,

L).

(ii)

Basis

is

an

clude the non-stretched

extension of basis

(i) to in1, possible (11,12)

coupling. With K 0,..., 1), (1 L) are also allowed. Though K is set to in basis zero (iii), the angular correlation can be taken into account through the cross term of the exponential part of the basis function. In bases (i) and (ii) the factors exp(- FbAx/2) are always "Correlationfree" in a particular channel, that is, it contains no cross term in the exponential part. In these bases it is through the inclusion of all rear-

(I

+

1, L

-

I +

rangement channels that type ment

for

(iii), (that

=

=

=

one

the contrary, is, coordinate

on

through the general

takes

one

care

of the correlation. In

set) explicitly;

case

(i)

contained in basis

form of A.

expected, the

re-

to other bases. The correlation

poor compared is too restricted to obtain

are

(i)

basis of

just any one arrangethe correlations are allowed

Table 8.11 shows the results of calculations. As sults with

a

needs to consider

a

realistic

description

of the system. The angular correlation, which is taken into account in basis (ii), certainly improves the energy over case (i). The basis functions

first six for L

(iii) give

figures 0

even

better

of the most

energies. In fact they reproduce the precise variational calculations [20, 23, 921

2 states. Even with K

0, the use of the full A matrix incorporate important correlations between the particles. A Gaussian basis of type (ii) is employed in the Coupled=

enables

--

one

to

=

the

Rearrangement-Channel Gaussian (CRCG) basis variational calculation of [201, where the angular part is, however, represented by the

176

Complements

coupling of type (6.3). The fact that the D state energy with the type (iii) calculation of dimension 200 becomes slightly lower than that of [20] with 1566 basis functions confirms the importance of successive

optimization of the nonlinear parameters. Further increase of the dimension can improve the accuracy rather easily in the angulax function of Eq. (6.4) as seen in the case of S and P states. The basis function used in [23, 921 is correlated exponential (CE) which a

caxeful

takes the form of

exp(-air,

-

T21

-

JT2

-

T31

-

7IT3 -'r1j)

for the orbital motion with

Multiorbital

nonzero plied by some polynomials determined The are momentum. by the , parameters a, -y angular calculations These 4.2.2. in Sect. random tempering explained using the exponential function give very precise results.

Table 8.11. The total

energies of the tdIL molecule. Parameter set a of by superscript b, where set

Table 8.2 is used except for the case indicated b is used. Atomic units are used. Dimension

E

200

-111.29346

200

-111.36398

200

-111.36444

600

-111.3645077

CRCG[20] CE[231

1442

-111.364507

1400

-111.364511474

(i) SVM (ii) SVM (iii) CE[231

200

-108.13122

200

-108-17914

200

-108-17940

1800

-108.1795424

800

-108-179361

CRCG[20]b CE[921b

2662

-108.179385

1900

-108.1793881

(iii)b CRCG[201b CE[921b

800

-99-660367

2662

-99.660548

1900

-99.6605507

SVM

(i) (ii) SVM (iii) CRCG[201

200

-103.37067

SVM

200

-103.40824

200

-103.40849

1566

-103.408481

L

Method

S

SVM SVM SVM

P

SVM

SW

P*

D

(i) (ii) (iii)

(ifl)

b

SVM

9.

Baryon spectroscopy

This

chapter is devoted to applications of the SVM to the constituent quark model of baryons. There are several different models of baxyons and this is a very hot topic nowadays. The discussion of the different models and their relative merits are far beyond the scope of this book, and our only aim here is to show the applicability of the SVM to solving tbree-body dynamics in constituent quark potential models. The constituent quark model assumes that the baryons comprise three quarks with dynamical quark masses and the quarks interact via phenomelogical potentials. These potentials contain a confining term and other terms which determine the fine structure of the spectra. are no free quarks observed in nature, the confining inter-

As there

action hinders the "ionization7 of the the

baryons in the constituent usually taken as a power

models. This interaction is

quark potential potential (V(r) rP). The second part of the interaction is traditionally chosen as the one-gluon exchange potential (OGEP) which is a color analogue of the Breit interaction of quantum electrodynamics (QED). There is an alternative possibility, the meson exchange interaction, which is motivated by the fact that, despite its quite successful reproduction of the ground-state spectra of the mesons and baryons, the OGEP may not be adequate for describing the excited states as mesonic effects or quark-antiquark excitations become important. This chapter includes examples for both choices to illustrate law

-

how the SVM

can

be used for these systems with different interac(nonrelavistic and semirelativistic) forms of

tions and with different

the kinetic energy. These simple quaxk models have obvious limitations

(e.g., large relativistic corrections can be anticipated for light quarks), but their success

indicates that relativistic and field theoretical effects

incorporated

in the paxameters. In

so

Y. Suzuki and K. Varga: LNPm 54, pp. 177 - 186, 1998 © Springer-Verlag Berlin Heidelberg 1998

far

as

are

somehow

sophisticated approaches

9.

178

Baryon spectroscopy

quantum chromodynamics (QCD) do not provide results for these systems, the application of constituent quark models is justified. based

on

9.1 The trial function in the constituent

quark

model carries space-, spin-, flavor-, and color degrees of freedoTn. The flavor is an extension of the isosphn to include up(u),

quark (q)

The

down(d), strange (s), charm(c), bottom(b),

and

top(t) quarks.

baxyons are colorless: The three quarks in a baryon form a color-singlet state, that is, they are totally antisymmetric with respect to the interchange of the color coordinates. For example, the eight baryons of spin 1/2, N (p, n), A, Z (Z+, V), Z-), and EF (EE,", belonging to a family of octet baryons, consist of three quarks of u, d and s flavor varieties. The product of the spin-, flavor-, and spacepart of their wave functions has to be symmetric to comply with the generalized Pauli principle. The spin paxt is represented by the spin functions X(S,,)Sm, (see Complement 6.5): The

TIT),

xmi a

X(O).1.1 22

2

r6 ( -V

11 X(1) 'TT

The flavor

IR

=

I (

S exp

where X and metrizer.

9.2

same

wave

-

I III)

functions

wave

baryons with the The trial

21111)

chaxge

function for

-1 -

are

2

are

-v/2

(I TIT)

-

I

ITT)), (9-1)

I ITT)

shown in Table 9.1, where the

arranged baxyons is a

are

in each column.

combination of the terms

6Ax) X(S12)SM (T12)TMT

the

(9.2)

spin and flavor functions, and S is

a

sym-

One-gluon exchange model

one-gluon exchange potential (OGEP) model has proved to be quite successful in describing the spectra of the ground states and

The

various

properties of

the

baryons [118, 119, 1201.

In this model the

9.2

Table 9. 1. Flavor to

wave

model

One-gluon exchange

ftmctions of baryons

179

arranged columnwise according

charge +2

Baryon N A

UUU

+1

0

uud

ddu

uud

ddu

-1

ddd

71,= (ud du) d + du) 71, 72 (u

A

-

s

2 '

UUS

dds

s

ssd

SSU

S?

SSS

7L (ud

Ac

-

2 ,

El-

72= (ud

UUC

+

du) c du) c

ddc

72 (ud

Ab

1

uub

Eb

vr2-

-

du)b

(ud + du) b

ddb

quarks exchange massless but color-charged gluons and the qq potenas the color analogue of the Breit interaction [3, 1211. Consequently, the simplest version of the OGEP includes a Coulomblike I/r piece and a color-magnetic ("hyperfine") piece:

tial is taken

7r -

i<j

6mimj

(AI7. AC j)(ffi-0j)j(rj-rj)'

where the Gell-Mann matrix

generator for the ith uct,

1:8

=1

introduce masses

dence,

(9-3)

S

quark

AF (a) AC (a). (In

A9 (a) (a

and

(A'9 Ajc) -

a more

tensor and other

spin-orbit,

=

z

is the color

SU(3)

scalar

prod-

stands for

a

elaborated framework order

higher

essentially

terms.)

one can

The

quark

very weak flavor depenflavor-blind. In a nonpertur-

mi in the denominator introduce

but the interaction is

8)

1,

a

bative treatment the contact interaction leads to

a

Because

singularity.

of this and because of the finite spatial extent of the constituent

quarks

the delta function should be smeared out, and it is to be substituted by a Gaussian or a Yukawa form factor.

Among the several different parametrizations of the OGEP we have potential [1221 as an example:

chosen the AM

3(A9 8

Vij H

-

A(7) 2rr.'

x

--+Ar-A+ r

3mpaj

exp

Tij ij 1.

7F 2

a

3

Pij

-

-

O'j

,

(9.4)

180

9.

Baryon spectroscopy

where the

length r is given in units of inverse energy (I fin 1/197.327 MeV-'), and the smearing parameter pij is given iTi the forioa Pij

=

-B

(

A

_

"

2mimj

mj + Taj

)

(9-5)

The

315 MeV, quark masses used in the calculation are Tn,, Tnd 577 MeV, m, 1836 MeV and ?nb 5227 MeV. The parameters m , were determined by a fit on a large sample of meson states in every ffavor sector [1221: They are n 0.1653 0.5069, rs' 1.8609, A GeV2 A 0.8321 GeV, B 0.2204 and A 1.6553 GeVB-'. The matrix element of the color part can be easily obtained because the baryons are in a color singlet state. By noting the relationship between the color-exchange operator P53 and (AF Ajc), =

=

=

=

=

=

=

=

=

=

=

7

-

PC== zy

2

C (A9-Af)+-, 3 '

(9.6)

J

the matrix element of

(A9.A'7) 3

between the

S

simply

to

states reduces

-8/3.

The SVM results

[1221

color-singlet

[81, 1231

are

compared

with the calculations of

in Table 9.2. The

agreement between the two results is good. data [1241 are included for guidance. One has to

The

experimental compaxe the energies relative to the nucleon ground state and one has to bear in mind that this potential gives good results for the mesons and no free parameter has been introduced to fit the baryons. Table 9.2. The

tial

[1221.

masses

of baryons

The numbers in

(in MeV)

parentheses

axe

as

the

predicted by the AU poten-

masses

relative to the nucleon

mass.

Baryon

Ref.

N

[1221

SVM

Experiment [1241

998

995

939

A, Z. Ab Zb

1154(156) 1231(233) 1343(345) 1674(676) 2296(1298) 2466(1468) 5642(4644) 5849(4851)

1306(311) 1149(154) 1228(233) 1339(344-) 1674(679) 2290(1295) 2467(1472) 5635(4640) 5849(4854)

1232(293) 1116.(177) 1192(253) 1318(379) 1672(733) 2285(1346) 2455(1516) 564150 (470250)

-Fb

5808(4810)

5803(4808)

A

A E

0

9.3

9.3

Meson-exchange

model

181

model

The OGEP model is successful in and

Meson-exchange

describing ground-state energies

properties of baryons, but for the excited

states

a

number of

delicate problems remain unsolved. No model has been able to

explain, orderings in light- and strange-baryon spectra in a simple three-quark description of baryons. The source of the problem can be easily understood by the following argument: The ground state of the nucleon N(939) has positive parity followed by the positive paxity 1/2+ Roper resonance N(1440) and the negative-parity 1/2- and 3/2- states N(1535) and N(1520), respectively. The parity of the states follows as (+, +, -, -). In the case of the A, the order of states follows a (+, -1 +1 -) pattern. The order of parity of the spectra in a simple harmonic-oscillator quark model is (+, -, +, In the case of the linear confinement the level spacing changes, but the order for

example,

the correct level

of states remains the

The

same.

wave

function of N and A differs

only in flavor, but the OGEP is flavor independent (though it slightly depends on flavor through the mass difference of light and strange quarks in Eq. (9.4)). Therefore it predicts the same level order for both N and A in contradiction to the experiments. To resolve this problem an explicitly flavor-dependent mesonexchange interaction has been introduced [1251. The essential difference between the two approaches is that while the OGEP of type (ai o-j) V(rij) acts on the color and spin space, the Ei<j (AF AjC) 3 -

-

%

meson-exchange potential Ei<j AFA- 37(aj-o-j)V(rjj) acts on the flavor and the spin degrees of freedom. The meson-exchange potential combined with a semirelativistic form of the kinetic energy is the second example of the application of the SVM for baryon spectroscopy. In this example no gluon-exchange mechanism is explicitly introduced to describe the qq interaction but only a meson-exchange potential is employed to generate the baryon '1

spectra. The

three-quark Hamiltonian is a sum of the semirelativistic Idmeson-exchange potential V and the confinement potential VO + Cr: netic energy, the

3

3

H=E /--2+ ?

Mi2 P71i +M?

where the

+

(Vii

meson-exchange potential

+

V"

+

Clri

V reads

as

-

ri

1)

(9.7)

9.

182

Baryon spectroscopy 7

3

Vij (r)

V7r (r)

=

ij

1: AF (a),XjF (a) + VI

a=4

+ VI7 (r) AF i (8) ij

The form factor of the

g2

f

1

47-,

2

AjF (8) + 3 Vj'j7' (r)

Oj

-

aj

meson-exchange potential

V

ij

AF i (a) AjF (a)

(r)

3

a=1

12mimj

2

I

6 -Ay

e-A-yr

A 'I

A2'Y

r

r

I

paxametrized

is

as

(9-9)

1

coupling constant gy is taken to be g8 for the pseudoscalar octet mesons (7r, K, n) or go for the pseudoscalar singlet meson (n,), respectively and the cut-off mass Ay is assumed to be given by

where the

Ay

=

Ao

(9.10)

+ riLy

q, 77. For the constituent quark masses we take the 500 MeV. Parameters typical vdues, Mu, Md 340 MeV and m, of the Hamiltonian are listed in Table 9.3.

for each -/

=

K,

-Ft,

=

=

=

Table 9.3. Parameters of the semirelativistic constituent

quark model with

meson-exchange potential Fixed parameters

Quark

masses

Meson

[MeVI

masses

[MeVI 928

Mui Md

M,

Ar

AK

An

A'a

340

500

139

494

547

958

41r

0.67

Free parameters

(golg8)2 1.34

Ao

[fin-]

K

Vf0 [Me,V

fln-21 2.33

-416

0.81

2.87

C

The -matrix elements of the semirelativistic kinetic energy in Eq. (9.7) can be calculated with the method presented In Sect. 7.6. The matrix elements of

culated

by-using

AF(a)AjF(a) 71

in the flavor space

Table 9.1 and the

explicit

can

be

easily

calm-

form of the GeH-Ma=

Meson-exchange model

9.3

183

matrices. It is useful to know the action of the

AF(a)A-3 (a)

ator

the flavor

on

wave

ffavor-changing operfunctions. As is summarized in

Z

9.4, for example the ffavor function uidj, when acted AF (a) M'(a), transforms to 2djuj uidj. I

Table

E

3

upon

by

-

a=

Z

3

Table 9.4. Effect of

Operator 3

flavor-changing operators

on

quark pairs

UU

dd

SS

ud

us

ds

Ar (a) X3 (a)

UU

dd

0

2du-ud

0

0

1

AF (a) AF j (a)

0

0

0

0

2su

2 sd

4

-1 UU

-1 dd

4UU

lud

-!us

-ids

3

3

Z

/\F(8),XjF(8)

3

3

3

3

_

predictions of this model axe shown for all light- and strange-baryons with mass up to M < 1850 MeV; the nucleon mass is normalized to its mass of 939 MeV, which determines the value of the confinement potential parameter V0. All masses corresponding to three- and four-star resonances in the most recent compilation of the Particle Data Group [124] are included. The result is good, reproducing the spectra of all low-lying light and strange baryons [123, 126]. In particular, the level ordering of the lowest positive- and negative-parity states in the nucleon spectrum is reproduced correctly, with the 1/2+ Roper resonance N(1440) falling well below the negative parity 1/2- and 3/2- states N(1535) and N(1520), respectively. Likewise, in the A and Z spectra the positive-parity 1/2+ excited baryons, A(1600) and E(1660), fall below the negative parity 1/2-In

3/2-

9.1 the SVM

Fig.

states,

A(1670)-A(1690),

and the

1/2-

state

E(1750),

respec-

tively. In the A spectrum, at the same time, the negative-parity 1/2-3/2- states A(1405)-A(1520) remain the lowest excitations above the A

ground

state.

remark is in order about the necessity of employing a semirelativistic kinetic energy operator in the three-quark Hamiltonian (9.7). Certainly, this is only an intermediate step toward a fully At this

place,

a

covariant treatment but it

already

allows

us

to include the kinemat-

ical relativistic effects. In any nonrelativistic approach these effects get compensated by the potential parameters, but there one faces a

disturbing

consequence of

constituent

quark

and

c

v1c > 1,

is the

where

velocity

of

v

is the

light.

mean

velocity of the

184

9.

Baryon spectroscopy

18001700-

El

E----1

L-J

=

16001500M

[MeV]

14001300-

12001100-

N

1000-

A

900-

1

1+

1-

3+

3

2

2

Y

Y

5+ 5 Y Y

1-

3+ 3i -2

Fig. 9.1. Comparison of low-lying baryon spectra predicted by the mesonexchange potential model with experiment. The solid lines denote the calculated spectra, and the shaded boxes show the error bars.

experimental

masses

with

their

(Continued

on

the next

page.)

One may think that the idea of the meson-exchange interaction acting between quarks is unfamiliar though it has produced the good results. To

judge

its merits the present calculations have to be

tended into several directions

ex-

(prediction physical observables, e.g. factors, decay widths, etc.). The complexity of the NN interaction is basically due to the compositeness of the nucleon. As N, A or Z belong to the same octet family, it is natural to attempt a unified description of the NN, AN or EN interaction from the underlying qq potentials. This goal is at present too difficult to achieve directly on the basis of QCD. In so of

form

far

as

QCD as yet presents no results, the effective theory formua microscopic quark-cluster model [1271 seems to be justified.

lated in

9.3

(Continued

from

Fig

Meson-exchange

model

185

9. 1.)

E] 1800

1700 1600

-

-

F-7

17.71

t

H

r--.7.

-

r__,_T

p G=

r_.j

0

p"

-

-

1500M

[MeVj

1400-

13001200-

1100-

A

1000900

1

1

_2

1

2

_2

_2

1+

1-

3+

1

_2

1800

1700 1600

1500 M

[MeVJ

1400

1300 1200 1100

1000

900 3-

1

11

3+

_2

_2

1

_2

186

The

9.

Baryon spectroscopy

intermediate-range

attraction of the

cannot be accounted for

by

tribution between the colorless the

baryon-baryon interactions produces no con-

the OGEP because it

It is not clear yet whether introduced above leads to a realistic de-

baryons.

meson-exchange potential scription of the NN interaction or not. It is probable that the OGEP combined with the meson-exchange potential is a useful, effective vehicle to obtain a reasonable description of both baxyon spectra and baryon-baxyon interactions at the same time. See, for example, [128] for the attempt along this line.

in solid state

10.

Few-body problems physics

This

chapter is a collection of examples of the application of the SVM to few-body problems in the field of solid state physics. The examples include excitonic complexes, biexcitons, and quantum dots with and without magnetic field. The biexciton and two

(or excitonic molecules), the bound state of two holes

electrons, provides

an

interesting few-body problem,

since it

may be thought as a positronium. or a hydrogen molecule with variable electron and hole masses realized in semiconductors. The biexcitons

also often confined and

are

can

be modelled

as

two-dimensional

(2D)

systems. In recent yeaxs there has been much excitement in the possible applications of ultrasmall. systems with a length scale of 10-100

A,("nanostructures"). The technological motivation (in electronics and optoelectronics)

is that the smaller components

to manufacture very small

contain

very few electrons

only a

are

faster. It is

possible

nanostructures, often called "dots", which

(N

<

10).

The

quantum-mechanical

effects in these small systems axe very important and their properties are strongly N-dependent. The energy spectra of few-particle quantum

dots call for theoretical interpretation. In confined in

are

a

box of sizes

L, L.,

a

nanostructure the electrons

and L,. If

L,

-

Ly

>>

L, the

quantum dot is quasi 2D. The confinement is usually modelled by a harmonic-oscillator potential. This system is somewhat similar to an atom in

nature, where the "confining" potential is the Coulomb

traction of the electrons to

quantum dots

are

Throughout this chapter

we use an

tron. When the dielectric constant of

length =

a

effective

mass

me*

for

material is denoted

an

by

elec-

r., the

and the energy will be measured in "atomic units" with Bohr h2n/ (M*e2 ) and haxtree (two times the Rydberg energy) e-

radius a*

2R*

at-

nucleus in the atom, and therefore the often referred to as "artificial atoms". a

=

e2/(Ka*), respectively.

Y. Suzuki and K. Varga: LNPm 54, pp. 187 - 211, 1998 © Springer-Verlag Berlin Heidelberg 1998

188

10.

Few-body problems

10.1 Excitonic

in solid state

physics

complexes

The excitonic

complexes have considerable importance in the development of semiconductor physics and spectroscopy. The bound state of a positively charged hole with an effective mass m and an electron with an effective mass m,* is called an exciton in semiconductor physics. The mass ratio ocan between 0 (hydrogenic limit cchange m*/m*h and oI (positronium limit) depending on the material and other factors. Like in the case of hydrogen, where not only the hydrogen atom but the hydrogen molecule (H2), or the H2+, H-, H,+ ions are bound, the system of N, electrons and Nh holes can also be bound. The latter system is called an excitonic complex. These excitonic complexes, including the charged excitons, have been subject of intensive experimental [105, 1291 and theoretical [99, 130-1351 investigation. The properties and structure of these systems strongly change with the mass ratio, and, by approaching the two limiting cases, one arrives at two completely different worlds. The interest in these systems has =

=

e

=

been intensified when the advance in semiconductor

technology has possible the fabrication of artificial nanostructures with diameters comparable to atomic distances. This restricted geometry has a prominent effect on the dynamics of the excitonic species. In the following we present the ground-state energy and some other properties of 2D excitonic complexes. The general Hamiltonian made

be written

can

IV.

H

as

N

pi,

i=1

2m,

i=IV'+I

N

j>i=N' +l x

TC.

r"Iri

-

e2

+

2Mh

3>z=l N,

e2

E where

Ne

pi,

+

=

N

e2

E E

rj I

i=1

j=N,+1

is the dielectric constant of the

material,

and the position

2D vectors in the xy plane. In atomic units introduced in this chapter, the Hamiltonian becomes dimensionless and the envectors

axe

depends only

(Note

that

do not need to

specify what dependence is hidden in the atomic units.) This is easily understood by introducing dimensionless coordinates and momenta by ri* ri/a* and pi* pil(hla*). Then the ergy

value of

K

on o-.

is used because the

r,

=

Hamiltonian

(10-1)

we

is reduced to

=

10.1 Excitonic N,

H

2

2P'

2

P

2(o-N,

i=N +I

+N

N

+ Z

i>i=l

3

-

N'-

E

+

j>i=N,+l

2

0-

*2

E

+

189

N

/

1

2R*

complexes

Jr

-

'r

7,

3

P'

N,) N

E E

I

i=1

j=N,+l

J'r j*

r 3

I'

At this point, a comment is due. What we consider here is a welldefined quantum-mechanical problem to be solved. This is, however,

experimental situation. In the realistic case there considered, for example the effect of other electronic bands, the possibility that the interaction is different from the pure Coulomb force due to the confinement in the z direction, etc. The discussion of the importance of these effects is beyond the scope only are

model of the

a

many other factors to be

of this book.

As the

problem here is practically the same as that discussed in the chapter of small atoms and molecules (Chap. 8), the same trial function is used (see Eq. (8.1)), except that it is tailored to the 2D case, that is, the position vectors have only x and y components. The results for case

o-

=

0 and

o-

=

1

are

and in Table 10.2 for the 2D

shown in Table 10.1 for the 3D

case.

between the 3D and 2D results is the

The most

large

striking difference binding

increase in the

0) in energy in the 2D case. E.g., the binding energy of R2 (with o2D is about 8 times of that in 3D. The increase of binding has been =

found

experimentally

Table 10. 1.

as

well.

Energies and binding energies (in a.u.) of 3D

of electrons and holes for two orbital

angular

cases

momentum and

of the

mass

ratio

o-.

exciton complexes

L and S

are

The asterisk refers to the states which

are

found to be unbound. The binding

energy is understood with respect to the nearest threshold.

E(o-i)

B(o-=O)

B(o-=I)

-0.500

-0.250

0.500

0.250

-0.528

-0.262

0.028

0.012

-0.602

-0.262

0.102

0.012

-1.174

-OM6

0.174

0.016

System

(L, S)

E(o-=O)

eh

(0,0) (0,1/2) (0,1/2) (0,0) (0,1/2) (0,1/2)

eeh ehh

eehh eeehh eehhh

*

-1.344

the total

spin of the exciton complex, respectively.

0.169

190

10.

Few-body problems

in solid state

physics

Table 10.2. Energies and binding energies (in a.u.) of 2D excito-n complexes of electrons and holes for two cases of the mass ratio o-. M is the z component of the total orbital angular momentum and S is the total spin. See also the caption of Table 10.1.

System

(M, S)

E

eh

(0,0) (0,1/2) (0,1/2) (0,0) (0,1/2) (0,1/2)

-2.00

-1.00

2.00

1.00

-2.24

-1.12

0.24

0.12

-2.82

-1.12

0.82

0.12

-5.33

-2.19

1.33

0.19

eeh ehh eehh eeehh

eehhh

(o-

=

0)

E

(o-

=

1)

B

(o-

*

-6-82

1.50

=

0)

B

(o-

=

1)

10.2

equality 2(r+-)

distances have to fullfil the

=

Quantum

dots

V(r--)2 + (r++)2.

191

Ta-

ble 10.3 shows that this is not satisfied. Moreover, the fact that the uncertainties

Arij

(,ri2j

-

(rij 2

are

large

means

that

no

such in-

terpretation is possible. There is only one case where the uncertainty is in very small, that is the distance between the (heavy) positive charges with accordance in that In can limit. case one the hydrogenic assume, the adiabatic approximation, that the positive charges are fixed at the distance of 0.37 a.u. The equilibrium distance in the H2 molecule in 3D is 1.4

a.u.

Table 10.3. ratio

mass

Average distances in 2D biexcitons (eehh) as a function of the E.g., (r--) is the mean distance between the two negative

o-.

charges. Atomic 0-

(r++) (,r+-) 2 (r _) (r 2+) 2 (r _)

=

0

units o-

are

0.4

=

used. a

=

0.7

0-

=

0.67

1.26

1.55

0.37

1.14

1.49

1.80

0.47

0.93

1.16

1.38

0.59

2.09

3.19

4.33

0.14

1.69

2.95

4.33

0.31

1.29

2.05

2.88

1.80

dots

10.2

Quantum

Rapid

advances in semiconductor

rication of nanostructures called

[136, 137, 1381. electrons,

are

In

I

quanturn dots

technology

have led to the fab-

quantum dots a

few

or

artificial atoms

electrons, typically

2 to 200

bound at semiconductor interfaces. These few-electron

(2D) electron gases (MOS) structures are

systems arise when homogeneous two-dimensional metal-oxide-semiconductor

of heterojunctions

or

laterally confined

to diameters

comparable

to the effective Bohr

ra-

dius of the host semiconductor. The interest in quantum dots arises not only from the prospect of new technological applications but also from the desire to understand the in

physics of a few interacting electrons

external field. Needless to say, we concentrate on the few-electron where the effect of electron-electron interaction and their corre-

an

case

lation

seems

to be very

important.

192

10.

Few-body problems

The axtificial atoms

in solid state

consider here

we

of N electrons confined in 2D

physics are

modelled

by

a

system

by harmonic-oscillator potential. Before starting with artificial atoms in 2D we present a calculation for the energies of 2D "natural" atoms where the "co-ofi-ohn ' potential is a

Coulombic. The results for few-electron atoms and ions Table 10.4. The much

binding energies

are

again, due

are

to the 2D

given

in

geometry,

than in the 3D

case. Otherwise the properties of these laxger systems axe rather similax to those of their 3D counterparts. For ex-

ample,

akin to

3D,

the

H, Li

or

Be atom

can

bind

an

electron,

extra

while the He atom cannot.

Table 10.4.

Energies

of atoms and ions confined in 2D. M is the

nent of the total orbital

units

are

(M, S)

H

(0,0) (0,1/2) (0,0) (0,1/2) (0,0)

He Li

Be

momentum and S is the total

z

compo-

spin. Atomic

used.

System

H-

angular

Energy -2.00000000 -2.24

-11-89 -29-87 -56.77

The

ex6mple of quantum dots considered here is a system of 2D electrons in a quadratic confiniD potential. The Hamiltonian reads as N

N

9

Pi

H

+

_M

2m*

(V__

+

ivy)

M

where v., and v.

by

N

I 2

e2

*WO2,r? +

(10.2)

exp( IiUr),

(10.3)

-

2

are

the

x

and y components of the 2D vector

v

defined

10.2

Quantum dots

193

N V

(10.4)

Uiri.

The parameters ui and A of the basis function SVMDue to the external field

are

determined

(the single-particle potential),

by the

the Hamil-

tonian (10.2) of the system is not translationally invariant. Correspondingly, the basis function (10.3) is written in terms of single-

particle coordinates instead of relative ones. This basis function depends on the center-of-mass coordinate, and the energy obtained will be the total energy of the system, unlike the previous cases where the energy of the center-of-mass motion was always subtracted. The case of the quadratic confinement is very special, because in that case the energy of the center-of-mass can be separated. In general, for an arbitrary single-particle potential, however, this cannot be done. 1 electron is trivial and its solution is a simple The case of N 2 an analytical solution exists for cerharmonic oscillator. For N I a.u., the ground state tain frequencies [139]. For example, for hwo which is 3 is precisely reproduced by the numerical cala.u., energy culation. Not surprisingly, as is shown in Table 10.5, if the quadratic =

=

=

confinement is strong, the spectrum is close to that of a harmonic oscillator. In the realistic cases (hwo < I a.u.), however, the eigen-

strongly deviate from those of the harmonic oscillator. This example illustrates the importance of these systems: by changing the confinement one can "tune" the properties of these artificial atoms.

values

Energies of N-electron quantum dots with the z component of angular momentum M and the total spin S. The numbers parentheses are the eigenvalues without Coulomb interaction. Atomic

Table 10.5.

the total orbital in

units

are

used.

N

(M, S)

hwo

2

(0,0) (0,1/2) (0,0)

3.000

212.198

7.220

525.12

3 4

Figure

=

I

hwo

(2.000) (5.000) 10.600 (6-000)

10.1 shows the

=

654.45

100

(200.00) (500.00) (600.00)

energies of the ground and excited

states

of the energy of a harinonic-oscillator quantum) of two electrons as a function of the inverse square root of the oscillator constant, -1/2 If there would be no Coulomb interaction between the elec-

(in units

(hwo)

.

10.

194

Few-body problems

in solid state

physics

trons, the energy divided by hwo would be given by lines parallel to the horizontal axis., The deviation from the

straight lines is entirely interesting feature is that states but the ground state

due to the Coulomb interaction. Another level

crossings

always

occur

remains M

between the excited

0.

12

10

8

6

4

2 0

2

4

6

8

10

(hcoo )-1/2 10.1.

Fig. potential

Energy

with

an

levels of two electrons confined

by

a

oscillator constant wo. Atomic units

harmonic-oscillator

are

-used.

Quantum dots

10.2

195

3.5 3.0 2.5

2.0 ;-4

t__I (14

1.5 1.0 0.5 0.0

1

Fig.

3

2

4

(a.u.)

r

10.2. Electron densities of two-electron

quantum dots

as a

function

origin. The solid, the dotted and the dashed 5, respectively. Atomic 0.2, hwo 2, and hwo

of the radial distance from the curves

units

correspond to hwo

are

used.

1.2

1.0

0.8

A

0.6

0.4

0.2

0.0 0

4

2

6

r

Fig.

8

10

(a.u.)

(dashed curve), four- (dotted curve), (solid curve) quantum dots. The oscillator frequency of the

10.3. Electron densities of two-

and six-electron

quadratic confining potential

is hwo

=

0.2. Atomic units

are

used.

196

Few-body problems

10.

in

solid state

physics

peak density inreases with the number of electrons, that is, the equilibrium configuration is realized on rings of expanding diameter. In the case of N=4 electrons, for example, the paxticles may move along a ring, while they are situated at the vertices of a square to TniniTni e the Coulomb repulsion.

10.3

dots in

Quantum

magnetic field

A dramatic feature axises when the quantum dots are subjected to magnetic fields: The ground states are stabilized into magic-number states. When the

state

Tn

from

jumps owing

to the combined effect of the electron correlation and

appear

the Pauli

agnitude of the magnetic field is vaxied, the ground magic number state to another. Magic numbers

one

principle [140].

The Hamiltonian of the system is N

N

I

I

H

=

E 2m* (pi + e-A,)2 + -

N

2

us assume

ward in the

z

2

Wd 'ri

e2

E

1' Iri

i>i=l

Let

2

,,

-M

-

C

+

given by

that

a

(10.5)

-,rj I*

homogeneous magnetic

field B is

direction. The above Hamiltonian

can

applied

down-

then be rewritten

in the form

H

P'

2

+

-m w

2

2m*

N

2-

r?-

1 -

2

hw,

Ii,

e2

rdri

-

rj I

where u),

eB/(m*c) is the cyclotron frequency and w

We

the

=

V/W--22. rl4+wo

ignored magnetic interaction energy due to the electron spin. See Complement 10.1 for details. It is shown there that the part of

the Hamiltonian

corresponding to the single-particle motion can easily

be diagonalized by the use of associated Laguerre polynomials. Depending on the strength of the magnetic field, both the single-particle

10.3

Quantum dots

in

motion and the correlation due to the Coulomb

sive roles in

determining

function is the

same as

197

repulsion play deci-

the structure of the quantum dots. The trial

in the

For the two-electron with the

magnetic field

previous

case our

solution

section.

calculation is in

perfect agreement

[1411. The spectrum of two elec0) is shown in Fig. 10.4. See also

in

given analytical spin-singlet state (S Complement 10.1. The harmonic-oscillator frequency wo is taken as 0.01 a.u. The most intriguing phenomenon seen is the level hwo crossing. Due to these level crossings, the ground state changes with the strength of the magnetic field. This is shown in a magnified scale on the right-hand side of Fig. 10.4. If there is no Coulomb interaction between the electrons, no level crossing occurs. trons in the

=

=

10.0 18 9.5

16

9.0 14 +It

+Z

8.5

12 8.0

10 7.5 8

7.0 0

1

2

3

4

0.0

0.5

1.0

1.5

2.0

2.5

(,)C/ ("0

(J)C/(00

10.4. Energy levels of a two-electron quantum dot in magnetic field function of the cyclotron frequency w,. The figure on the right-hand side magnifies the level crossing. The oscillator frequency of the quadratic 0. Atomic units are 0.01. The total spin is S confining potential is hwo

Fig. as a

=

=

used.

Figures

plot the energy levels of a three-electron total spin being S 3/2) against the orbital

10.5 and 10.6

quantum dot

(with

the

=

198

10.

in solid state

Few-body problems

physics

25

20

15

10

5 0

2

4

6

8

10

12

14

COC/ coo 1.0.5.

Fig. z

Energy

levels of

a

three-electron quantum dot

component of the total orbital angular

IVI

=

6

(dotted curve),

and M

=

9

momentum M

(dashed curve)

frequency of the quadratic confining potential S

=

3/2.

Atomic units

are

used,

is hwc)

belonging

=

3

to the

(solid c=e),

orbital motion. The =

1. The total

spin

is

10.3

Quantum

3

4

dots in

magnetic

field

199

15

14--1

13

12

44

10-

9

8

7

6 0

2

1

5

6

7

9

8

10

M

Energy levels as a function of the z component of the total angular momentum, M, of a three-electron quantum dot in a low 3/2. Atomic 1). The total spin is S 0.2, hwo magnetic field (hw,

Fig.

10.6.

orbital

=

units

are

used.

=

=

200

10.

Few-body problems

of these orbits

in solid state

physics

larger (see Eq. (10.16)). The energy of the dots interplay of the single-paxticle energies and the interaction energy. By increasing the strength of the magnetic field, similarly to the case of low magnetic field, the ground state does -not take all possible values of M. By changing the magnetic field the states with M 3,6,9,12,... "magic numbers' become ground states. is determined

axe

by

the

=

40-

35-

30-

25

-

201

10

0

1

2

3

4

5

6

7

8

9

M 1.0.7. The

Fig. hwo

=

1).

same as

Atomic units

in

are

Fig.

10.6 but for

high magnetic

field

(hw,-

=

6,

used.

change of the ground-state angular momentum quantum numbers as a function of the magnetic-field strength is illustrated In Fig 10.5 for a three-electron quantum dot with spin S 3/2. This figure shows the energies of the states with M 3 (solid curve), M 6 M and 9 orbital The calmomentum. angular (dotted) (dashed) culation shows that by changing the strength of the magnetic field the orbital angulax momentum of the ground state of this system is M 3 for w,lw < 5, it is M 6 for 5 < w,lw < 11, and then it The

=

=

=

=

=

switches

=

over

to M

=

9, reproducing the "magic number"

sequence

10.3

(M

3,6,9,..).

Quantum dots

in

magnetic field

201

States with other orbital

angular momentum never ground state and are not included in the figure. The previous examples dealt with spin polaxized electrons (S 3/2). Actually, spin polarized (S 3/2) and spin unpolarized (S 1/2) states compete to be the ground state as the magnetic field changes. This very interesting phenomenon is illustrated in Fig. 10.8. As the magnetic field increases, the ground state changes as (M, S) (1, 1/2) -+ (2,1/2) --+ (3,3/2) and so on. At low magnetic field the lowest energy state is spin unpolarized (S 1/2) and as the magnetic field increases the spin becomes polaxized. The orbital angular momentum (M) changes continuously (in steps of unity). =

become the

=

=

=

=

=

5

4

3

C5

2

0 0.0

0.5

1.0

1.5

2.0

2.5

(j)C/ (1)0 1-0.8. Spin (S) and z component of the total orbital angular momentum (M) quantum numbers of the ground state of a three-electron quantum dot

Fig. as

a

function of

denote M and

magnetic field strength. hwo S, respectively. Atomic units are

=

1. Solid and dotted lines

used.

202

10.

10.4

Few-body problems

Quantum

in solid state

physics

dots in the generator coordinate

method In Sects. 10.2 and 10.3 the correlated Gaussian basis of

Eq. (10.3)

is

to obtain the solution of the

employed not the only

quantum dots. However, th is is Gaussian basis function for the quantum dots. In fact, the

quantum dots offer

(8.9)

that

was

application of another basis function study of small molecules. That basis func-

very nice

a

used for the

by the matrix A which describes the correlated particles and also by the generator coordinates s which represent several peaks of the density distribution of the

tion is characterized motion of the

allow

us

to

system. In this section

consider the quantum dots in 3D and

we

field. The

state of the

quantum dot

apply belong

can ground 3angular momentum (for example, in the N electron case). The application of the basis function (8.9) gives a very simple way to obtain accurate energies of the dots even with nonzero orbital angular momentum, without the hassle of partial-wave expansion or angular momentum algebra. As this basis function has no definite orbital angular momentum, in principle one has to project out the component with good angular momentum quantum numbers. In practice, however, the converged wave function already belongs to the correct ground-state quantum numbers and the energy gain due to an orbital angular momentum projection is negligible. As the Hamil2 tonian and the L operator commute, the optimization of the wave 2 function filters out the eigenstate of L as well. As was mentioned in Sect. 6.1, this type of calculation is called a variation before projection. In the limit that the variational trial function is chosen to be flexible enough, the solution of this type of calculation would reach the 2 eigenstate of the conserved quantity like L to a good approximation.

no

to

magnetic

nonzero

orbital

=

In Table 10.6 the results of the SVM with the basis function of

Eq. (8.9)

is

compared

to that of

The shell model works

a

extremely

large

scale shell-model calculation.

well in this

case

because the

con-

fining potential is a harmonic-oscillator well. By choosing the singleparticle wave functions to be the eigenfunctions of this single-paxticle potential, the diagonalization of the Hamiltonian with the relatively weak Coulomb interaction between the electrons is simple and gives an accurate solution. The results of the two methods are in perfect agreement. This agreement shows that the optimization of the basis of

Eq. (8.9) finds the

correct

ground

state

automatically

even

for the

10.4

case

with

sis size is

Quantum

nonzero

dots in the generator coordinate method

orbital

angular

sufficiently large. An

momentum

orbital

angular

provided

203

that the ba-

momentum

projection

may lead to a faster convergence, but as it can only be carried out by a three-dimensional numerical integration, it would prohibitively slow

down the calculation.

Energies of few-electron quantum dots in 3D calculated by SVM and by a large scale shell-model (SM) basis'. L is the total orbital angular momentum, S the total spin, and -x is the parity. K is the basis 0.5. Atomic units are used. dimension. hwo Table 10.6.

=

N

(L, S, -ri)

(1,1/2,-) 4(0,0,+) 5 (1,1/2,-) 3

a

P.

(SM)

K

E

4.01324

100

4.01324

6.35025

300

6.3506

39 hwo 14 hwo

9.00331

500

9.0032

6 hwo

E

(SVM)

Navratil, private

communication.

SM space

(in hwo)

Complements

204

Complements 10.1 Two-dimensional electron motion in

a

magnetic field

vaxiational solution to the

have

presented a previous section we few-body problems of quantum dots. In this approach a correlated Gaussian basis has been used and the problem has been formulated In a relative coordinate framework. The examples from atomic physics (Chap. 8) convincingly prove that this is a very powerful -way to cope In the

with the correlation between the electrons in the field of

an

attractive

only possible approach. One can, alternatively, use a basis set made up from products of single-particle states to diagonalize the Hamiltonian. The properties of these singleparticle states axe discussed in this Complement. The Hamiltonian of interest is given by center. This is,

H

however,

-2m*

not the

(P eAi)2 +

+

9*ABB

c

-

2

aj

I

+

vori)

2

(10.7)

+ X

i 'i

1ri

-,rj I

where m* is the effective electron mass, AB eh/(2m,c) the Bohr magneton of the electron, g* the effective g-factor of the electron, =

and

r.

is the dielectric constant of the bulk material. The

magnetic

interaction energy due to the electron spin is included in the Hamilltonian. The magnetic field is directed downward in the z direction, i.e. B

B

-

with B

> 0. For high magnetic field of, e.g. T, the value of ILBB becomes 0.5788 meV. The vectors ri

10

and pi

(0, 0, -B)

=

axe

2D vectors, which have

x

and y components. The

one-

body potential V(r) is to confine the quantum dots and is chosen to be quadratic, m* W02T 2/2. A typical value of the confinement en5 meV. By taking a symmetric gauge vector potential, ergy is hwo -

A

-r x

=

(P

B/2 2

e

)

_Ji2' j +

A

+

where A

B(y/2, -x/2, 0),

c

_2B 2

we

e. hB

2

(10.8)

4C2 +

_ey2-

and I-, is the

obtain

c

z

component of the angular

mo-

mentum.

To express the Hamiltonian in terms of dimensionless introduce

vaxiables,

-we

C10.1 Two-dimensional electron motion in

e,B W,

W

=

WC2

=

M

a

magnetic field

205

hI + W02

and

p

.

=

(10.9)

W U)

Here wc is the cyclotron frequency and p is the that the magnetic length is expressed by p

magnetic length. (Note using Bohr and hartree 2R*.) Then the Hamiltonian is expressed by the =

radius a*

- -2R*-1hwa*

dimensionless variable ri: 1

H

=

hw

A,

+

2

1

lr,2 2

hw, 2

E lj ,

-

2

g*AB B

aj ,

i

e2

+XE 1ri

with -

j>i

Here the is

hwc

=

length is

rjI

2R*a*

(10.10)

-

=

P

rIP

in unit of the

(2ra,/m*)ABB.

X

magnetic length. The cyclotron energy

The ratio of m,/rn* is of order 15 for the 2D

electron system in GaAs-Ga,,All-,,As heterojunctions. The strength of the Coulomb potential is of the order of X, while the level spacing of the single-particle energy is determined by hw. Therefore the ratio

Xlhw

-

VI'2--R*-Ihw is

the

quantity which

charac-

terizes the electronic motion. If the ratio is much smaller than

the

independent

tion. As it

the

motion of the electrons becomes

a

unity, good approxima-

increases, the correlated motion of the electrons overwhelms

independent

motion.

Recall that the second and third terms of the above Hamiltonian are

consistent with the well-known fact that

mass

M and

charge

qe in the

magnetic

a

spin 1/2 particle with magnetic

ffied B has the

interaction energy -IPB, where the magnetic moment tL of the particle is in general expressed by tL g1l + gs in units of ehl(2Mc). Here g, and g, are the respective gyromagnetic ratios for the orbital and =

spin angular momenta. The gi value is equal to q, while the Dirac 2q for a point charged paxticle like the equation would give g, 2.0023 ILB for the The measurement electron. gives I g, I precision electron and the deviation from 2 can be very accurately computed by the higher order corrections of quantum electrodynamics. On the other hand, the experimental values for the nucleons are far from the 5.586 for the proton Dirac value expected for point paxticles: g, =

=

=

and g, AN

=

=

-3.826 for the neutron in units of the nuclear

eh/(2mpc).

nucleon.

magneton

This fact is ascribed to the internal structure of the

206

Complements

The eigenvalue of the single-particle Hamiltonian, Ho hw (-,A/2 +r2 /2) -(hw,12)1., -(g*p.BB12)o-,,, is obtained easily. Rewriting the spatial coordinate as a complex variable z (x iy)/-\/-2, we defme =

-

I

at

72= (

=

0),

*

Z

-

'0

I

--.,f2- (z- OZ* ),

bt=

(z

a=

OZ

=

[at, b]

Hamiltonian

Ho

=

=

[at, bt]

=

OZ*

(z*

b

0 +

OZ

[a, at]

with the commutation relations

[a, bt]

+

0. We

can

[b, bt]

=

=

[a, b]

1 and

then express the

single-particle

as

hw(ata + btb + 1)

Ihw,(ata

-

-

2

btb)

Ig*ttBBc-z-

-

2

(10.12)

The operator at creates a right circular quantum of counterclockwise rotation about z axis, and bt creates a left one. Let a non-negative

eigenvalue of the total oscillator quanta ata+btb at a b b. and m denote an eigenvalue of the angular momentum 1,, Then the eigenvalues of A and btb are given by (N + m)/2 and (N m)/2, respectively. Since they should be positive integers or zero, the possible values of m for a given N are m -N+ N, N-2, N-4, 2, -N. The single-particle energy becomes integer N denote

an

=

-

-

=

...,

I

E,,,,,,

=

hw(N+1)

hwm

-

-

2

g*ABBS,

I =

with Sz

quanta

hw(2n + Iml

being

either

N is set

1/2

For

of

hw(N + 1),

1) or

to N

equal given N, possible

n.

a

+

hwm

-

-

2

-1/2, =

2n +

values of

(10.13)

g*ABB$,

and where the number of total

Iml

with

n are

0,

1

a

non-negative integer [N12]. The energies

....

with N + I-fold

degeneracy, corresponding to the 2D are independent of m conforming to N. The singleparticle energy is shown in Fig. 10.9. In the case of no magnetic field or very weak magnetic field (w,lwo < 1) the single-particle level shows a shell structure with degeneracy of N + 1. The single-particle level is then in the order of haxmonic-oscillator

(n, m)

=

(0, 0); (0, 1), (0, -1); (0, 2), (1, 0), (0, -2);...

The level

cross-

V/-I/-2

ing of the low-lying single-particle levels occurs at W,/WO 0.71 and the level with (n, m) (0, 2) becomes lower than the =

=

with

(0, -1).

Z-'

one

CIO. 1 Two-dimensional electron motion in

a

magnetic field

207

If wo 0, that is, there is no confining potential present or the magnetic field is very high (wc.Iwo > 1), w is (nearly) equal to (112)w, and the energy becomes E,,,,, hw,(n+(Iml -m)/2+1/2) -9*ABBS,, de=

=

(Iml

pending only

on n +

dent of m for

positive

-

m.

m) /2. Clearly the energy becomes indepen-

This

gives

rise to

infinitely degenerate levels

called the Landau levels with the Landau level index The fact that the

levels with

an

single-electron degeneracy

infinite

motion is

quantized

number in the

+

n

case

(IM I

-

m) /2.

to the Landau

of

no

confining

potential reflects the fact that the energy is independent of the center of the cyclotron motion. In the presence of the confining potential, the

single-particle energy increases with m as seen from Fig. 10.9. By using the polar coordinates r and 6 the eigenfimetions single-particle Hamiltonian are expressed as

rp2

ni n!

(n-t TP 2(n+lml)!

(r)

1-1

L (I ' 1) n

P

r2

(p2

-

r

ey-P

of the

2

2p2

(10.14) where

Ln(c) (x)

is

an

associated

Laguerre polynomial defined by

d L,(,o I (X) =ex-' (e-XX n+a n! dXn n

E k! (n

'k=O

F(n+a+l) (-X),. k)! -V(k + a + 1)

(10.15)

-

parity operation changes V to V + 7, so the parity of the singleparticle eigenfunction is given by (-l)'. For the lowest Landau states (n 0, m > 0) the larger angular momentum state corresponds to a wave function which is more extended from the origin:

The

=

2

(0o,jr loom

(Iral

The Han-d1tonian

+

1)P2.

(10.10)

(10.16)

contains the Coulomb interaction be-

electrons, which leads to interesting effects on quantum interplay between the magnetic field and the Coulomb interaction is an essential ingredient for studying the dots. The relative importance of various pieces of the Hamiltonian depends on m*, K, g*,

tween the

dots. The

and B. For two electrons the Hamiltonian

can

be

separated in the relative By introducing

and center-of-mass coordinates of the two electrons. the coordinates

7 C)

Is 6

5

4

3

2

1

0 0

1

2

3

4

5

6

7

8

9

10

O)C /0)0

Fig. 10.9. The single-particle energy E,,,,, of a quantum dot as a function of magnetic field strength. The Zeeman spin splitting of the energy is not included.

C10.1 Two-dimensional electron motion in

I

R=

-\f2-

('rl +r2),

Ir

a

magnetic field

I-(Irl -r2),

=

209

(10.17)

A/2

the Hamiltonian is reduced to H

=

hwf

I

,AR

-

+

2

1R21

'&V,, IR ,

-

"A'r + 21,r2 2

+ hW

hWcl

,T Z

2

-

C

.

2

2

g*[tBB(Sj,,

+

S2 ,)

X 1 +

(10.18)

-

vF2 r

by exactly the same Hamiltonian as the single-particle Hamiltonian and its energy and eigenfunction are given by Eqs. (10.13) and (10.14). The eigenfunction b(T) of the relative motion Hamiltonian may be obtained in polar coordinates. By separating the angular part as b(r) u(r)e " (m and the the function radial eigenvalue E, are obu(r) 0, 1, 2, ...), tained from the following equation The center-of-mass motion is determined

=

d2u

1 du +

-

.-

r

where

u(r)

r2

+

hW

dr

has to

M2

V2-X 1 +

satisfy

=

2Er

W, 7n

U

-

=

0,

(10.19)

r

the condition that its norm,

fo' drru(r)2, is

finite.

analytical solutions are available provided Xlhw belongs to a certain enumarably infinite set of values [1411. For a general case we can obtain the eigenvalue by numerical integrations. The eigenvalue 0, 1, 2,... for each m. We may be labelled by a quantum number n note the symmetry property of the eigenfunctions. The interchange of the position coordinates ri and V2 leads to r -r, which is # + 7r. Therefore the eigenfunction equivalent to the change of 6 and labelled by n m receives a phase change e"' (-I)m, so that it is symmetric for even m and antisymmetric, for odd m. Figure 10.10 displays the energy E, of the relative motion as a function of the cyclotron frequency. The most striking feature is the level crossing in the lowest level (ground state). With increasing magnetic field the so (0, 0) to (0, 1), (0, 2), (0, 3), ground state changes from (n, m) that the angular momentum m of the ground state increases one by one. (This figure is basically the same as Fig. 10.4 which is obtained by the variational calculation, but included here to show the significant Paxticular

=

---).

--*

=

=

role of the Coulomb

Finally

we

electrons in

a

..

-,

interaction.)

importance of the correlated motion of strong magnetic field has already been recognized in

note that the

the quantum Hall effect

[1421.

The

broadening of the Landau levels

210

Complements 12-

11

10I f I I

9-

8 It

7

*11

IA 41/

*, -

3-

2

1

0

-

1

0

1

2

3

4

5 0) C

Fig. dot

6

7

8

9

10

/ (00

10.10. The energy E, of the relative motion of a two-electron quantum function of magnetic field strength. The Zeeman spin splitting of

as a

the energy is not included. The solid curves are for states with even m and the dashed curves for states with odd m. hwo = 1. Atomic units are used.

CIOA Two-dimensional electron motion in is caused

by

scatterers such

as

a

magnetic field

211

impurities and lattice defects. The repulsion between many electrons

correlations due to the Coulomb

lead to the Anderson localization and the fractional quantum Hall effect. Laughlin [1431 successfully used a correlated basis of Jastrow

type

to describe the electron motion.

11. Nuclear

few-body systems

originally developed to solve physics. In this chapter we collect a

The stochastic variational method

was

few-body problems in nuclear few possible applications of the SVM for nuclear systems. The nuclear force, due to the effect of the underlying quark structure and relativistic motion, is a very complicated interaction. h addition to the spinisospin dependent central part, the two-nucleon interaction contains spin-orbit and tensor forces, and L2- and (LS)2_dependent terms. The two-body interaction designed to fit the nucleon-nucleon phase shift and the properties of the deuteron fails to reproduce the binding energies of the three- and four-nucleon nuclei, and a three-body interaction has to be introduced to get the correct binding energy. As the nucleons are not structureless point-like entities, the spatial part of the nuclear force contains a strong repulsion at short distances. These circumstances altogether make the solution of the nuclear few-body problem a

formidable task.

application is restricted to central forces. These schematic forces are used in simple model calculations and serve for benchmark tests. Examples of more realistic problems are shown J-n the last secThe first

tion.

Introductory remark

11.1

on

nucleon-nucleon

potentials The nucleon

(N)

has

spin and isospin degrees of freedom

in addition

of Eq. (2.3) is a product of these spatial one. The operator 0?. V factors, one acting on each coordinate of the three types:

to the

0?. 73

=

(0,,ij (space) 0,.ij (spin) -

Oij (isospin),

Y. Suzuki and K. Varga: LNPm 54, pp. 213 - 246, 1998 © Springer-Verlag Berlin Heidelberg 1998

214

11. Nuclear

where,

e.g.,

few-body systems

0,,,,j (space) (IL

=

n,

r.

-

-K)

1,

is

a

spherical tensor a scalar product

spatial part, and product (-I)"A/2__K+ I[T,,, x U,,Ioo, which (T,,,.U,,) is defined with Clebsch-Gordan coefficients by operator of rank

acting

K

in the

stands for the tensor

[Tr-1

X

Ur-2]r-393

=

E

(11.2)

rv1jL1K2A2jK3A3 >TK,jL1 Ur-2/L2'

<

IIIA2

e.g., [2, 70, 71, 72] for angular momentum algebra. The NIV interaction is a typical example of the strong interaction

See,

and is still not known in fiiU detail. There are, however, several versions of the nuclear potential whose parameters have been determined fairly

accurately so

to

as

reproduce two-nucleon

bound state and

scattering

data. The nuclear force reaches at most up to 2 fla (I fin = 10-13 cm). An NN potential which is consistent with the scattering data is called

"realistic". The most important ingredients of the realistic include central, ,tensor, and spin-orbit components. The central part of the nents:

0-'12

is thus

==

Ii

TTT27 0'1*(7'2,

expressed

V12

=

potential

is characterized

and(71'72) (o-j-a2).

potential

by four compopotential

The central

as

+ V' (,r) -rl'72 + VCO_ (r) 01 0'2

V(,r)

*

-

+ VcTO

(r) (Irl 72) (Ol U2) *

*

expressed by the space- (Pj'2), spin1+'rr72 and isospin-exchange (P172) operators. (P12 2 2 The generalized Pauli principle requires the relation These

components

can

also be

=

Pi2P12'P12_

=

Therefore the central force

VI 2

=

V12

=

(11.4)

_1* can

also be written

VB H Pl' 2

VW H

+

VM (r) PJ'2

(V-t (r)

+

V` (r) 7, '72) S12)

+

+

as

VH (r) PI'2 PI 2,

(11.5)

(11.6)

11.1

remark

Introductory

nucleon-nucleon

on

potentials

215

with the tensor operator 3 (o-1

S12

*

f6) (0`2 f6) *

U1 Cr2 *

/E4T (Y2

"

V

The deuteron

X

5

consisting of

bound through the force. Here

-

a

0212) (p)

proton

and

coupling of the 3SI and 3D,

2s+'Lj

neutron

a

waves

(n)

becomes

due to the tensor

denotes the two-nucleon channel with the

spin S

and the relative orbital

angular momentum L being coupled to the However, no such coupling occurs in the case of two protons or two neutrons because the Pauli principle (11.4) forbids two like nucleons with L 0 or 2 to be in a spin-singlet state. The interaction between like nucleons is just too weak to produce a total

angular

momentum J.

=

bound state. The

spin-orbit force has non-vanishing matrix elements only spin-triplet states, too. It is parametrized in the form V12

=

in

(Vb (r) + Vb-r (r) -ri '72) (L S) 12 -

with

(L-S)12

r X

2h

h

where p

=

-ih-L, ar

(r

X

hl

(PI

-

P2))

P)' (Ol + 2

=

(r

x

p),

2

(Ol

+

6'2))

and

(

Cr2)

2 x

)

(Ol

472))

+

indicates

a

product. The form factors of the various components pressed in terms of Y(x) e-xlx and its derivatives.

vector

are

(outer)

usually

ex-

=

As is evident from the above

discussion, one of the characteristic features of the realistic NN potential is its strong state-dependence, namely it differs in the four states of singlet-even, triplet-even, singletodd, and triplet-odd character, where even and odd refer to the parity of the orbital motion.

The tensor force makes it necessary to introduce at least D-waves in the calculations. Another important feature of the most commonly used

family of NN potentials is the strong repulsion at short distances, say within 0.5 fi-n. This requires due care in so far as short-range correlations must be properly taken into account in theoretical models. All of these aspects of the NN interaction really make a variational calculation for a nuclear system very challenging. In these circumstances

11. Nuclear

216

few-body systems

frequent to use some "effective" potentials which axe not necessarily designed to reproduce the scattering data but determined to fit some bulk properties of nuclei such as the binding energy and the size. Although relativistic effects should be fairly large in nuclei ((V/C)2 0.08, which is estimated from the kinetic energy TF 40 MeV belonging to the Fermi level), the ambiguity of the nuclear force makes it rather difficult to extract these clearly from experimental it is rather

-

-

data. The

complexity

of the NN interaction is due to the

substructure of the nucleon

as was

compositeness of mesons exchanged

11.2 Few-nucleon

discussed in

Chapt.

quark-gluon 9 and to the

between the nucleons.

systems with central forces

performance of the SVM by performing model calpotentials, e.g., the spin-averaged Malffiet-Tjon (MT-V) potential [1441, the Volkov no. I (Vi) "supersoft" core potential [1451, the Afnan-Tang S3 (ATS3) potential [1461, the Afinnesota potential [1471 and the Brink-Boeker (BI) potential [1481. Parameters of these potentials are given in Table 11.1. Some of these model problems have already been solved to high accuracy by various methods and therefore we can directly compare the solutions. The results presented in this section do not include the contribution from the Coulomb potential. Each calculation has been repeated several times staxting from different random points to check the convergence. The energy as a function of the number of basis states is shown in Fig. 11.1 for the case of 6Li with the V1 potential. The energies on different random paths approach each other after a few initial steps, and converge to the final solution. The energy difference between two random paths as well as the tangent of the curves give us some information on the accuracy of the method for a given size of the basis. The root-meansquare (rms) radius is calculated in each step and found to be rapidly convergent to its final value. By increasing the basis size the results can be arbitraxily improved when needed. The number of basis states required to reach energy convergence increases with the number of particles, but it depends on the form of We have tested the

culations with different NN central

well. This latter property is illustrated in of the alpha-paxticle. The soft-core Volkov (Vi)

the interaction for the

case

as

Fig. 11.2 potential

11.2 Few-nucleon

systems with central forces

217

Table 11J. List of the parameters of the nucleon-nucleon central po-

tentials. The potential consists of a few terms; each is expressed as Vf (IL, r)(W + MP' + BP' + HP'P'). See Eq. (11.5). For the Gaussian

potentials (VI, ATS3, Minnesota, Bj), the form factor f ([L, r) is eXp(_/tr2)' the potential strength V is in units of MeV, and the potential range p is in units Of fM -2, while for the Yukawa potential (MT-V) f (A, r) is defined by exp(-[tr)/r, V is given in units of MeVfin, and IL is in units of fin-, respectively. The Majorana, mixtures m and m' are set equal to zero in the calculation. For realistic values of m and n see the original papers. The parameter u of the Minnesota potential is set equal to unity. V

A

W

M

B

H

MT-V

1458.05

3.11

1

0

0

0

[1441

-578.09

1.55

1

0

0

0

VI

144.86

0.82

[1451

-83-34

1.60

ATS3

1000.0

[1461

-326.7

Potential

-2

M

M

0

0

1-M

M

0

0

3.0

1

0

0

0

1.05

0.5

0

0.5

0

-166.0

0.80

0.5

0

-0.5

0

-43.0

0.60

0.5

0

0.5

0

-23.0

0.40

0.5

0

-0.5

0

u/2 u/4 u/4

(2 (2 (2

-2

Minnesota

200.0

1.487

[1471

-178.0

0.639

-91.85

0.465

Bi

389.5

0.7

[1481

-140.6

1.4-2

shows

-2

rapid convergence, requires more basis states

1

-

I-M 1

-

n

while the to

get

an

-

-

-

u)/2 0 u)/4 u/4 u)/4 -u/4

0

(2 u)/4 (-2 + u) /4 -

M

0

0

MI

0

0

repulsive-core ATS3

interaction

accurate solution. The

relatively

fast convergence for the MT-V potential of a strong repulsion can be explained by the simplicity of the spin-independence of this interaction.

results, together with results of others, potential to N=2-7-nucleon systems. application 41.47 MeV fi-n2. In the table the ground-state enerWe chose h2/m E and matter rms radii (r 2)1/2 are given. The basis dimenpoint gies sion K of the SVM listed in the table is such that, beyond it, the energy and the radius do not change in the digits shown. For three-body systems, the solution of the Faddeev equation is known to be the method of choice (see Sect. 5.3), but the SVM can easily yield energy of the Table 11.2 shows the SVM

of the MT-V

for the

=

11. Nuclear

218

few-body systems

-65.5 -65.6 -65.7 -65.8

5

-65.9

0)

-: W

-66.0

-66.1 -66.2 -66.3

-66.4 -66.E 0

50

100

150

200

250

300

350

40(

dimension of the basis

Fig.

11.1.

Volkov

Convergence

of the

(VI) potential [145]

6Li

energy

on

different random

paths.

The

is used.

-29.0

-29.5-

Minnesota

................................................................. -30.0-

ATS3 2

Vo-lkov

-30.5-

W

-31.0

MTV -31.5

-32.0

0

20

40

60

80

100

120

140

16(

dimension of the basis

Fig. 11.2. Convergence potentials

of the

alpha-particle

energy for different central

11.2 Few-nucleon

systems with central forces

219

Energies (in MeV) and root-mean-square (rms) radii (in fin) of interacting via the Malfliet-Tjon (MT-V) potential [14 . The value of K denotes the basis dimension beyond which the energies and the radii of the SVM calculation do not change in the digits shown. Table 11.2.

N-nucleon systems

N

(L, S) J'

Method

E

(T 2)1/2

2

(0,1)1+

Numerical

-0.4107

3.743

SVM

-0.4107

3.743

3

4

(0,1/2)1/2+ Faddeev[150, 1511

(0,0)0+1

(0,0)0+ 2 5

6

7

(1,1/2)3/2-

(0,0)0+ (1,1/2)3/2-

5

-8.25273

ATMS[121 CHH[1521 GFMC[411 VMC[1531a

-8.26

SVM

-8.2527

FY[1491 ATMS[121 CRCG[261 GFMC[411 VMC[1531a

-31.36

SVM

-31.360

CRCG[261

-8.50

2000

SVM

-8.49

150

ZLO-01

1.682

-8.26

0.01

1.682

-8.27

0.03

1.68

-8.240

1.682

80

1.40

-31.36 -31.357

1000

-31.3

0.2

-31.3

0.05

1.36 1.39 1.4087

150

VMC[153]a

-42.98

SVM

-43.48

VMC[1531a

-66-34

SVM

-66.68

1.52

800

SVM

-83.4

1.68

1300

'Calculated with Coulomb tracted

K

perturbatively.

The

0.16

1.51 1.51

0.29

500

1.50

potential, the Coulomb contribution then subpotential strength used in the VMC [153] cal-

-578.17 MeV, which is culation is Vi=1458.25 and V2 from that used in the calculation. See Table 11.1. =

slightly different

220

11. Nuclear

few-body systems

accuracy. As the MT-V potential is a preferred benchmark test of the few-body calculations, there are numerous solutions available. same

Table 11.2 includes

a

few of the most accurate results. The nice agree-

ment for the four-nucleon case corroborates the fact that the SVM is as

accurate

as

the direct solution of the

Faddeev-Yakubovsky (FY) Amalgamation of Two-body corre-

equations [1491, Multiple Scattering (ATMS) [121 the method of the

lations into

Carlo

[411

(VMC) [153]

methods. The basis used in the

Gaussian-basis the

SVM,

or

the variational Monte

and the Green's function Monte Carlo

(CRCG)

(GFMC)

Coupled-Rearrangement-Channel.

variational method

[26]

but the Gaussian parameters follow

is similar to that of

geometric progressions. ground

The fact that the basis size needed in the SVM for both the

and first excited states of the four-nucleon system is much smaller proves the efficiency of the selection procedure. See Chap. 4. The re-

sults of the VMC calculation for the five- and six-nucleon systems are also in good agreement with the results of the SVM- The MT-V potential has no exchange term; therefore, unlike nature, it renders the

five-nucleon system

bound,

and the nucleus tends to

collapse

the

as

binding energy increases with the number of particles. Neither the MT-V nor the V, potential contains the full set of change components of the central potential, rather simple. The Minnesota potential, spin-,

and

isospin-exchange

realistic. In fact it has been

so

ex-

the calculation becomes

however,

contains space-, and is considered to be more operators,

successfully

used in

microscopic cluster-

model calculations tential

was

[28, 29, 301. An extensive calculation with this pocarried out for N=2-6 nucleon systems in [31], where all

possible spin and isospin configurations were allowed for and all angula.r functions that give non-negligible contributions were included. The agreement with experiment was surprisingly good. The energies and the'radii of the triton and the alpha-particle converge to realistic values. The Minnesota potential, correctly, does not bind the N=5 system, but it binds 6He and slightly overbinds ILL The radius of 6He is found to be much larger than that of 4He, consistent with the neutron-halo structure of 6He

[29, 301.

The SVM calculation of

[311

has

made it

possible to test for the first time the Minnesota force without assuming any cluster structure or restricting the model space by any

other bias.

The last

example

is the

application

to Efimov states

how well the correlated Gaussian basis describes the totics. A

three-body system

with

short-range

[1541

few-body

to show asymp-

forces may have several

11.2 Few-nucleon systems with central forces

221

bound states. If the

two-body subsystem has just one bound state (close to) zero, the three particles can interact at long

whose energy is distances and an infinite number of bound states may appear in the three-body system. These "Efimov states" are extremely interesting

experimental and theoretical points of view because of their distinctive properties. These states are very loosely bound and their wave functions extend far beyond those of normal states. By increasing the strength of the two-body interactions these states disappear. from both

A system of three identical bosons of nucleonic mass is considered for simplicity. The potential between the particles is taken as the Poeschl-Teller interaction because this

can

be

easily

V(r) Here

r

potential

is

analytically

solv-

body case, and therefore the two-body binding energy

able for the two-

set to zero;

625.972

1251-943

sinh(l.586 r)2

cosh(I.586 r)2

(11.10)

in MeV.

=

is in units of fi-n. A

spatially

very extended basis is needed to

represent the

bound states. In this

basis. The

basis is created

predefined diagonal elements of the matrix A. These diagonal elements are taken as geometric progression:

wealdy predefined

case we use a

by using only

the

1

A,-,

(i

-

('

-

(aoq6

1))2

=

1,

...,

n),

1

A22

(j

-

( ao q(j-'))2 10

This construction defines

(i, A 0.1,

(I, I),-, (n, n).

=

q0

2.4. One

=

an n

can

=

reveal

2-dimensional basis corresponding are chosen as n 20, ao =

to =

find the first three Efimov states with this

can

expJ-2vJ

more

(11.11)

The parameters

basis size. The ratios of the

Ei+IlEi

n).

rule

energies of the bound states follow the [1541. By increasing the basis size one

bound excited states. Note that the value of

roughly corresponds to the spatial extension basis in this example goes out up to aoqon-I

aoqo'-'

of the basis. The present =

0.1

x

2.419

=

1674990

This extension is necessary to get the third bound state. For a comparison, to calculate the ground-state energy of -4.81 MeV it 7 and the basis covers only the [0, 101 (fi-n) is enough to choose n

(fin).

=

interval. The

rms

radii of the

ground, first and

second excited states

are about 1.5, 25 and 6000 fin, respectively. As shown in Fig. 11.3, these facts illustrate the tremendous spatial extension of the Efimov

222

11. Nuclear

few-body systems

Ground state

.0 .0 0 10.0

Efimov state

0.1

0.0 M

x

Fig. IXM,

Wave fimetion

amplitudes

of the

ground

state and the first

Efimov'stAte. Note the different scale (in fin) of the lengths of the Jacobi coordinates

x

and y.

11.3 Realistic

223

potentials

states. These results indicate that the extended correlated Gaussian

basis

gives

a

practical

to describe the

means

tics of the Efimov states. See

Complement

asymptotics characterispossibility of

11.4 for the

Efimov states in the 12C nucleus.

11.3 Realistic

potentials

The trial function is

given

as a

combination of the correlated Gaus-

sians:

'O(LS)JMTMT(-'C 14) 1

Ajexp(- 1.+,Ax) [OL (X)

=

XSJ jM

X

2

where

x

=

jX1i

...

XN-11

is

a

TITMTli

set of relative

(11.12)

(Jacobi) coordinates,

the operator A is an antisymmetrizer,, XsMs is the spin nTmTis the isospin function. The matrix A is an (N

-

symmetric, positive-definite

function, and

1)

x

(N

-

1)

matrix of nonlinear variational parame-

angular part of the wave function. It is taken as a vector coupled product of partial waves i3)]L123 I LML This is re[[[Yli 41) X Y12 (ZAL12 X Yls (X3 OLML (X) ferred to as the method of partial-wave expansion. The spin and isospin functions are also successively coupled, for example XSM,

OLML (x) represents

ters. The function

the

:`

...

.

=

X(E12SI23 )SMs ...

we

L

used the

=

0, 1,

satisf3 g

2.

=

[[[XI/2

X

XI/21SI2

partial-wave channels For the alpha-particle,

the condition 11 +

12

+

X

X1/21S1,23 ...J,sms

with

(11, 12)L,

For the

triton,

where 1i < 2 and

partial waves ((11, 12) L 12 13) L 13 :! 4, 1i :! _ 2, 111 121 <

all

1

-

0, 1, 2 have been tried. As the triton has J 1/2, there are three spin and two isospin chan1/2 and T 0, 1. For the alphanels; (S12)S (0)1/2,(1)1/2,(1)3/2 and T12 0, T 0) there are six spin and two isospin chanparticle (J nels unless very small isospin mixing is taken into account; (S12 S123) L12 !

11

+

12 and L

-

=

=

=

=

7

(0, 1/2)0,(0,1/2)1,(1,1/2)0,(1,1/2)1,(1,3/2)1,(1,3/2)2 T123) (0, 1/2), (1, 1/2). =

and

(T12,

=

dependence of realistic nucleon-nucleon interaction is extremely important. To extend the application of the SVM calculations to nuclear systems interacting with realistic potentials, in addition to the previously applied random selection of the nonlinear parameters of the correlated Gaussian, a random selection of the spin and orbital components of the wave function The

spin, isospin and orbital angular

momentum

11. Nuclear

224

few-body system

is introduced. The main motivation for the random selection is that

the numbers of channels and nonlinear parameters are prohibitively large, therefore the calculation of all of the matrix elements and di-

potentially important basis states is out alpha-particle, for example, there partial-wave channels even in our truncated-partial wave expansion. Just to show up an alternative, it is worthwhile assessing what dimensions a deterrni-ni tic optimization would require. The simplest choice of the nonlineax parameters of the Gaussian basis is to use a diagonal matrix A. One of the best deterministic choices for the diagonal elements is a geometric progression [251. To reach good accuracy, at least five values for each of AJ-1 A22 3 125 functions in a given and A33 have to be used, requiring 5 channel. The spin-isospin and space paxt, therefore, would result in a all

agonalization including

of the question. In the case of the are 12 spin-isospin channels and 32

7

=

basis size of about a

one

hundred thousand

"direct" calculation for the

(2

125

x

x

12

x

in such

32)

alpha-particle.

The literature is very rich in papers devoted to few-nucleon prob3 nuclei it is possible lems [155, 156, 157, 12, 25, 158-1611. For N =

to include

enough

performed, N

4 nuclei

=

channels and

but other methods some

results of the

an

exact Faddeev calculation

the

give essentially

of these methods become too calculations agree

existing

only

same

complicated,

within

a

can

be

results. For

and the

few hundred

keV.

To test the SVM

used two, from the

we

form,

rather different interactions. The

(AV6

and

ond,

AV8) [1621,

the Reid

is

a

the

first,

view of

spatial Argonne potential

well-behaved smooth function. The

potential (M) [1631

linear combination of

point of

is

more

singulax

exp(_/tr2)/,rk-type terms.

sec-

and includes

a

The latter

potential AV6 The includes can certainly cause some problems. potential only central and tensor components and serves as a good test case for the inclusion of non-central forces. The AV6 and AV8 potentials axe used without Coulomb potential, while in the case of the RV8 potential the Coulomb interaction is added. To

keep

the number of nonlinear parameters

matrix A to be

diagonal

in

one

of the

possible

low,

we

restricted the

Jacobi coordinate sets.

of the three-nucleon system we have only one possibility of the Jacobi coordinate, (NIV) + N. For the alpha-particle we use

In the

case

possible coordinate sets, (3N) + N ("K") and (2N) + (2N)type ("IF) Jacobi coordinates. Note that the basis function is fuHy both

antisymmetrized.

This choice is also dictated

by physical

intuition

as

11.3 Realistic

it is natural to consider

potentials

225

3H+P 3He+n and d+d-type partitions in the ,

Test calculations show that tbis choice

alpha-paxticle. satisfactory results.

already gives

As is shown in Table

11.3, the convergence is relatively fast both for the triton and the alpha-particle with the AV6 and AV8 potentials, but in the case of the RV8 potential, due to its singular nature and stronger repulsive core, the convergence is slower. About 50 basis states for the triton and about 200 basis states for the alpha-particle give fairly good binding energies. The energy of the alpha-paxticle with the basis size of 200 is already within 0.5 MeV of its final value. It is very satisfactory that the SVM has succeeded in reproducing a reasonably good energy with just 400 basis states.

Table 11.3. The convergence of energies alpha-particle for different potentials, AV6

(in MeV)

[1621,

for the triton and the

AV8

[1621,

and RV8

[163].

K is the basis dhnension.

'He

311 K

AV6

AV8

RV8

K

AV6

AV8

RV8

25

-6.63

-7.36

50

-7.04

-7.69

-6-53

100

-24-37

-25.15

-23-35

-7.41

200

-25.05

-25.50

75

-7.11

-24.15

-7.74

-7.54

300

-25.28

-25.60

100

-7.15

-24.35

-7-79

-7.59

400

-25.40

-25.62

-24.49

The results of the SVM and other calculations Tables

11.4 and

11-5. We show and compare

compared in the results not only are

for the energy but for the rms radius and average kinetic and potential energies as well. The results remain the same by repeating the calculations several times

staxting from different random values.

comparison for the triton with RV8 demonstrates that the SVM are in very good agreement with the Faddeev results. Since Faddeev calculations are considered exact for three-body systems (see The

results

Sect.

this agreement confirms that the basis selection of the SVM performed efficiently even for the singular potential of RV8.

5.3),

has been

The correlated

hyperspherical

harmonics

(CHH) expansion

method

(see 5.2) also agrees with the SVM for the triton. The results of the SVM and GFMC are very close to each other. Except for the case Sect.

of the

alpha-particle

the statistical

errors

AV6, the energies of the SVM axe within of the GFMC, though the expectation values of with

11. Nuclear

226

few-body systems

Table 11.4. Energies (in MeV) and radii (in fin) of the triton calculated by different methods and with different interactions. (T), (V), and (V6) are the expectation values of the kinetic energy, the total potential energy, and the of the central and tensor components, respectively. (, 2) 1/2 denotes the root-mean-square radius. The value of PL shows the percentage of the component with the total orbital angular momentum L.

potential energy

SVM

Faddeev

GFMC

CHH

VMC

AV6

(T) (V6) (r 2 1/2

44.8

PS PP PD

91.2

E

-7.15

-51.9 1.76

-43-7(1-0) 1.95(0.03)

-52.0(3.00) 1.75(0.10)

< 0.1

8.7

-7.22(0.12)a

-7.15'

-6.33(0.05)'

AV8

(T) (V6) (VLS) (T 2)1/2

46.3

PS PP PD

91.1

E

-7.79

-52.9 -1.2

1.75 < 0.1

8.9

_7.79d

-7.79'

RV8

(T (V) (T 2)1/2

52.2

PS PP PD

90.3

E

-7-59

aRef.

-59.8

1.75

54.0(0.20) -62.0(0.20) 1.68(0.07)

52.2

-7.54(0. 10)b

-7. 59b

-59.8

1.76

< 0.1

9.7

[1641 bRef. [1651. .

'Ref.

-7.44(0.03)'

[1571. dRef. [1591.

'Ref.

[1611.

-7-60'

11.3 Realistic

potentials

227

Table 11.5. Energies (in MeV) and radii (in fin) of the alpha-particle by different methods and with different interactions. The isospin mixing due to the Coulomb potential is not taken into account. See also the caption of

Table 11.4. SVM

CHH

vMC

FY

GFMC

AV6

(T) (W) (r 2)1/2

100.1

-125.4 1.49

PS PP PD

84.3

E

-25.40

-122.0(3.0) 1.50(0.04)

-122.0(1.0) 1.50(0.01)

-25.50(0.20)a

-22.75(0.01)a

0.5 15.1

AV8

(T) M (W) (VLS) (r 2)1/2

98.8

PS PP PD

85.5

0.3

E

-25.62

-25.75(0.05)

111.7

109.2(0.20) -137.5(0.20) 2.45(0.23) 0.71(0.02) 1.53(0.02)

-124.4

-124.20(l.0)

-121.5

-2.9 1.50

1.51(0.01)

14.2 ,d

-25.60'

-25.31-

RV8

(T) (V6) (VLS) (KOUI) (T 2)1/2

-139.1 2.1

0.75 1.51

84.1

PS PP PD

0.4 15.5

15.5(0.20)

E

-24.49

-24.55(0.13)b

aRef.

[1641. bRef. [165].

cRef.

-23.79f

[1571 dRef. [1591 .

-24.01e

.

eRef.

-23-9c

[1611. fRef. [1551.

11. Nuclear

228

the kinetic and the

few-body systems

potential energies

VMC and GFMC have

a

integration. Though the of the trial function

statistical error

well,

as

are

error

somewhat different. Both

bar of VMC is influenced

the

error

by the

choice

of GFMC is considered

purely

statistical in the limit of infinitesimal time step (see Sect. 5.1). Variational calculations were considered to be inappropriate

realistic

not be able to

for

the

reproduce large potential energies [1581. Our calculation shows that, with the careful optimization of the nonlinear potentials,

as

they might

of

involved in the Monte Carlo

cancellation between the kinetic and the

variational parameters, this is not the case. We energies even in the case of the RV8 potential.

can

obtain accurate

experimental energies of the triton and the alplia-particle are MeV, respectively. We see that the calculation using the realistic potentials underbinds; about 0.9 MeV for the triton and about 3.8 MeV for the alpha-particle. This indicates that the binding energies of few-nucleon systems cannot be accounted for in two-nucleon potential models but call for other mechanism to get more attraction. One possibility for the mechanism is a three-body potential which can be produced by two-pion exchanges among three nucleons. Once we have a basis for a given potential, one naturally expects that the same basis may give fair ground-state energy for other potentials of similar nature as well. We have checked if it is really the case. The basis optimized for the RV8 potential gives excellent results (within 100 keV) for AV6 and AV8 as well. Due to the singular nature and stronger repulsive core of RV8, however, the basis optimized for AV8 gives about 500 keV less binding for the alpha-particle with RV8 than the basis optimized for RV8 itself. This result is still not so bad and can be easily improved by refining the nonlinear parameters as explained in Sect. 4.2. Therefore, one does not have to look for an entirely new basis set for another interaction, but can use the same basis for a given system, with some "fine tuning" if necessary. It is obviously important to calculate accurate binding energies of light nuclei with realistic forces. For example, the two-neutron separation energy of 6He is about I MeV, so that a few hundred keV less binding is thought to change its neutron "halo" structure significantly. One of the advantages of the SVM is that it is relatively easy to extend it to N 5-, 6-, 7-nucleon systems [31]. The low dimension of the bases required to solve the N 3- and 4-nucleon problems The

-8.48 and -28.295

=

=

confirms that the SVM is suitable for

treating larger

nuclei with

alistic forces. The formalism and the computer code itself is

re-

general

11.3 Realistic

[311,

so

potentials

229

applicability is mostly limited by the memory and speed of no dffficulty in including three-body

the

the available computer. There is forces if necessary.

utility of the global vector representation of Eq. (6.4) in describing the angular part of the system interacting via realistic potentials. We calculated the ground-state energies of the triton and the alpha-particle by using the AV6 interaction [162]. The results by the global vector representation and by the partial-wave expansion are compared to each other in Table 11.6. The model space allows for natural parity states only. The partial-wave expansion is restricted for partial waves with orbital angular momentum 0, 1 and 2. These partial waves give a good description of the ground states of these We show the

nuclei the

even

The table shows that

[321.

global

vector

in the

more

different orbital

one can

reach the

same

results with

representation as with the partial-wave expansion complicated case when the tensor force couples the

angular

momenta. The

nice illustration of the main

case

of the

alpha-particle

is

a

of the

global vector representaadvantage partial-wave expansion: Even in the expansion truncated to the natural parity states, one needs 24 partial-wave combinations due to the large number of combinations of the individual partial waves, while in the global vector representation only 4 sets of (K, L) ((K, L) (0, 0), (1, 0), (0, 2), (1, 2)) were used to reproduce the same result [1661. By increasing the number of particles the partial-wave expansion would contain a prohibitively large number of combinations. The number of sets (K, L), on the contrary, does not depend on the number of particles. Only the number of parameters ui increases (linearly) by adding particles to the system. tion

over

the

=

energies of the ground states of the triton and the alphaparticle [1621. Only natural parity states have been taken into account for the orbital motion. Two types of angular functions are used; the global vector representation (GVR) and the paxtial-wave expansion (PVVE). K is the basis dimension. Table 3-1.6. Total

with the AV6 interaction

3

411

11 Method

K

GVR

100

PWE

100

Method

K

E

-6.80

GVR

300

-23.29

-6.80

PWE

300

-23.27

E

(MeV)

(MeV)

230

Complements

Complements 11.1 Correlations in

few-nucleon systems significance of the correlation we calculate the binding energies of the triton and the alpha-particle by using the correlated Gaussians and the correlated Gaussian-type geminals. The spinisospin parts of the triton and the alpha-particle wave functions are considered totally antisymmetric and, as the nucleon is a fermion, their spatial parts must be totally symmetric. The spatial motion in the ground state of the N 3- or 4-nucleon system may thus be To elucidate the

=

treated

as

motion of bosons. We obtain variational solutions for the

triton and the

alpha-partile interacting via a spin-isospi-n independent two-nucleon potential. The orbital wave function is assumed to be given by combinations, of the correlated Gaussians with L 0, see Sect. 7.2: =

Tf

CkS eXP

(_2

,7c A k X

k=1

Here

x

is the Jacobi coordinate set and S is

positive-definite symmetric

matrices

Ak

a

symmetrizer. Each of the

contains nonlinear variational

parameters, three for the triton and six for the alpha-axticle. The

paxameters

can

be determined

with the code of chosen

so as

[811.

was

done

The number K of the basis functions has been

1V =

function,

The function

Ffj (-v)'Iexp( P,

a

(Gaussians),

one

may

try the following

corre-

3

-

product

1Vri2).

2

IF

tions

The calculation

to reach convergence.

As another type of trial lated wave function

Tl'= F P

by the SVM.

of the nodeless harmonic-oscillator func-

describes the

independent single-particle motion,

whereas the function F takes into account the correlations. The

Jastrow-type correlation factor [471

is

taken,

as

IV

F=

(I+aexpj-b(rj

fj

_

ri)21

i>i=l KN

E ak exp (__2 i;BkT') k=1

in

a

single Gaussian form,

CILI Correlations in few-nudeon systems

with KIv

231

1, where ak is given by an integer power of a, and Bk is an N x N symmetric matrix of type, 2b Ei uiiii, where ui is an N-dimensional vector which has only two nonzero elements. =

2

2

Therefore the trial function TJ- becomes lated

Gaussian-type geminals (6.26)

needed formulas for matrix elements

a

with

combination of the

n

=

0 and R

=

corre-

0, and the

involving such special geminals

in that section. Three parameters v, a, and b can be varied to minimize the energy. Note that Tf is totally symmetric and that were

given

the center-of-mass coordinate x1v can be factored out from the intrinsic motion. This makes it possible to calculate the

its

dependence

on

intrinsic energy. We also consider contains

only

the

a special type of the correlation factor which pair correlation

K

F2

=

I +

N

1: ak

exp

bk (ri

_,rj)2)

k=1

Here the

pair correlation

can

be better described with combinations

of K Gaussian functions than with

Jastrow-type

correlation becomes

correlations of ear

more

than two

parameters bk and

v

Eq. (11.15). more

It is

useful in

particles play

a

where various

major role. The nonlin-

and linear parameters ak

minimize the energy. We use three potentials, the MT-V

expected that the

cases

are

[1441, V, [1451

determined to

and B,

[1481*

potentials listed in Table 11.1. The space exchange operator PI of the potential can be set equal to unity because of the bosonic symmetry of the

spatial wave function. The Majorana mixture parameters.

energy is thus

independent

Table 11.7 summarizes the results. The result for N

[311

=

of the

3 and 4

calculated with the correlated Gaussian basis is known to be in

good agreement with other accurate calculations available in the literature. It is interesting to note that, except for the alpha-article with the MT-V potential, the pair correlation with K 2 terms-already gives lower energy than the Jastrow-type correlation described with a single Gaussian function. (The alpha-paxticle has more compact structure than the triton. Because of this property, the strong repulsion of the MT-IT potential has to be fully taken caxe of in order to obtain the ground-state energy particularly for the alpha-particle. The correlation factor of Jastrow type appears to be more suited than just the pair correlation of Eq. (11.16) in this regard.) The small difference =

Complements

232

between K tion

can

=

2 and K

pair correladescription of

3 calculations indicates that the

=

well be described with two Gaussians. A better

pair correlation appears to be important. The trial function with K 0 is nothing but a product of the single-particle wave functions the

=

and contaiins

no

lot of energy. This potentials such a.-, the MT-

correlation. This function misses

evident in

a

singular significant energy difference between potential. MT-V potential. This suggests that with the results the CG asid CGG at least a triple particle correlation, e.g.,

becomes

more

more

Note that there is

V

a

IV

E

exp(

-

b(Tj

-

Tj)'

-

b(Tj

-

Tk

)2

-

b(Tk

_

T,)2),

(11.17)

k>j>i=l

has to be taken into account in the correlation factor for this potential to obtain accurate energy. This problem was investigated in [1671, which takes into account the two-, three- and even more-particle correlations and shows the importance of triplet correlations in producing accurate energy.

Table 11.7.

Energies

thealpha-particla in

of the triton and

the correlated

(CG) of Eq. (11-13) and the correlated Gaussian-type geminals (CGG) of Eq. (11.14), which axe chosen to represent correlations in one of two forms. The correlation factor F of CGG is defined by Eq. (11.15) for Jastrow and by Eq. (11.16) for the number K of pair correlations. See Table Gaussians

11.1 for the nucleon-nucleon

potential.

The

am

in units of MeV.

CGG

CG

MT-V

energies

Jastrow

K

=

0

K=I

K=2

K=3

[1441

triton

-8.25

-6.00

unbound

-5.78

-7.11

-7.27

alpha

-31.36

-29.04

-6.41

-27-03

-28.47

-28.93

triton

-8.46

-6.99

-6.66

-6-99

-8-11

-8-11

alpha

-30.42

-29.14

-27.92

-29.13

-30-06

-30-13

triton

-11.64

-9.95

-7-00

-9.87

-11.20

-11.20

,alpha

-38.34

-36.73

-28.19

-36.02

-37.60

-37.60

V1

B1

[1451

[1481

spin-isospin dependence, the correlation state-dependent. The evaluation of matrix

When the interaction has factor is also

expected

to be

CII.2

of

Convergence

partial-wave expansions

elements with such correlation factors would then be

Refer to related

11.2

[1681

for

a

recent

development

on

the

more

application

233

involved.

of the

cor-

functions to heavier nuclei.

wave

Convergence of partial-wave expansions

Here we examine the convergence of the partial-wave

expansion (PVVE)

bound-state solution for

in

obtaining few-body systems. We consider examples of three-body systems consisting of p, n, and n (triton) or of p, n, and a hyperon A. The A is a neutral baryon with mass mAO 1116 MeV. It has spin 1/2, isospin 0 and strangeness -1. The NA interaction is not strong enough to form a bound state between a nucleon and a A. When one or few A's are embedded in a nucleus, they form a bound system called a A hypernucleus. The simplest hywhich is called a hypertriton pernucleus is the (p, n, A) system 3H, A and its ground state has P 1/2+. The binding energy of 3A H is 2.4 MeV from the three-particle threshold. As neither subsystem of pA nor nA forms a bound state, A couples weakly with p and n. In fact the A separation energy of 3A 1-1 is only about 0.2 MeV. Most of the binding energy of 3A 11 thus comes from that of the pn subsystem, namely the ground-state energy is just =

=

0.2 MeV below the threshold of deuteron to

attempt

to describe the

the coordinates

xI

=

rp

-

ground-state r, and X2

(d) +A. wave

(I'P

=

+

It would be natural

function Tf in terms of

Tn)/2

-

rA.

simplify the analysis we assume that the pn subsystem has the same spin and isospin state as d, that is spin 1 and isospin 0. This assumption, known to be a rather good approximation, leads us to To

the condition that Tf must be we assume

an even

that the total orbital

angular

function of xI. In addition momentum of the system is

zero, and that the three 1/2 spins are coupled to J 1/2. Under these in Tf be follows: can general expressed as assumptions =

Tf

=

f (XI

I

X2, XI

*

X2) [xi (pn)

x

X.L

(A)].LM,

2

2

where the space part f is a function Of X1, X2 and X1'X2. For Tf to be an even function of xI, f has to be an even function Of Xl'X2The Hamiltonian of the system is

given by

H=T+V

h2

a2

h2

192

---

21L, ax,

2

21L2 C9X2 2

+

Vpn

+

VpA + VnAI

Complements

234

where IL1

and A2 2MNMj1(2MN + IVIA). Only the central is included in the Hamiltonian. The pn interaction VP" in

=

potential the triplet u

1

=

MN12,

even

state is taken from the Minnesota

Table

(see

=

11.1).

The NA central

potential

potential [147]

with

is assumed to have

the form of Minnesota type

VNA=

x

I VR+I(I+Po')Vt+-(I-P -)V 2 2

(lu+ 1(2-u)P')

(11.20)

2

2

with

VR The

u

=

2

VORe-ISRT2,

value is set

Vt

equal

they

are

-Vfote-""

to 1.5. We

-Vfoe-S' 2. (11.21)

V,

1

assume

that the

pA

interaction

the same, though there is some evidence hi fact slightly different. The potential parameters are

and the nA interaction

that

=

are

3, 4 binding-energy data: The strength 109.8, and Vo, 200.0, Vot parameters in units of MeV axe VOR h3j-2 of in units the and are 0.7864, and 1.638, nt r,-,R 121.3, ranges 0.7513, respectively. This NA potential will be used in the next ms determined

so as

to fit A

=

=

=

=

=

=

=

Complement to calculate the binding energies of s-shell hypernuclei. The equation of motion for f (XIi X27 XI *X2) is obtained by substi0 and tuting Eq. (11.18) into the Schr6dinger equation (H E)Tf the to coordinates. the Owing symmetry propspin integrating over of and the function of the wave assumption VpA VnA, we only erty element matrix the evaluate need to of, say VnA. The matrix elspin ement of PI exchanging the spin coordinates of the nA pair can be calculated by rewriting the spin function of Eq. (11.18), expressed in (pn)A coupling order, to that of the p(nA) order by using the Racah coefficient in unitary form (see Complement 6.3): =

-

=

[Xj(pn)xX.j(A)j.iM= 2

2

1: U(-!-!.!1;IS)[X.L(p)xXs(nA)].jM 2222

2

2

S=0'1

Vf3_ 2

1

[X.L (p) x Xo (nA) I.LM + 2

2

2

[Xi(p)xXj(nA)jjM. 2

2

Then the desired matrix element is

&1(pn) xx.L(A)ji].LMjP'j[xj(pn) 2

2

2

x

X.L(A)jfljm) 2

2

2

(11.22)

C11.2

Convergence

of

235

partial-wave expansions

1 .1 .1 .1; is) 1.1.1; IS) U( 2222 1) S+I- U(I:2222

.1.

(11.23)

2

S

The

equation of motion for f reads h2

a2

h2

a2

-

2A2 19X2 2

21L1- axi 2

I

+V,A(IX2

x,

-

2

+

1, P)

Vp. (XI)

-

E

boundary condition that f VpA(r, P') is given by

with the Here

VpA (r, P')

VR +

as

f (XI

One has to note that P'

i

X2 i

(I

1 X2 +

2

XI'X2)

has to vanish for

1Vt + 4

4

VpA

+

3V,) (lu

=

0,

large

(11.24)

xl_ and X2-

1(2 u)P')

+

-

2

2

exchanges rp

XII,P

(11.25)

and rA, which induces the

transformation of the coordinates: x, --+ x1/2 X21 X2 --+ -3x,/4 X2/2. The potential V,,A(r, P') is defined in exactly the same manner,

-

-

where pr

now

and

3xj/4

ground-state energy and the solution

of Eq.

transforms x, and X2 to

xl_/2 + X2

-

X2/2,

respectively. We obtain the

The variational trial function may be chosen correlated Gaussians (CG) of Eq. (7.3):

as a

(11.24).

combination of the

K

f(XliX2iXI*X2)

=

ECkfFAk(X) +FPAkP(X)II

(11.26)

k=1

1

where the second term with P

function is

an even

(0

0

-1

)

function of xj, Le.., for A

assures

All A12

that the trial

A12 A22

PAP

-A12 All A22 -A12 It is interesting to analyse the paxtial-wave contents of the solution. For this purpose we calculate the quantity becomes PAP

2

C1

=(f(XliX27Xl*X2)lpllf(Xl7X27Xl*X2))

(11.27)

with

PI

=

I[yl(XI)

X

YI(X2)j00)([YI(Xl)

X

Yl(X2)1001-

(11.28)

236

Complements

The result is

given

in Table 11.8. The admixtures of

D, G andhigher

waves axe small and the PWE is very effective in the present case. The root-mean-square (rms) radius of the hypertriton is calculated to be

4.87 fm. The

fm,

distance between the proton and the neutron is 3.61 which is slightly smaller th an the corresponding distance (3-90 fin) rms

obtained for the free

deuteron,

and the

distance between the A

rms

and the center-of-mass of the proton and the neutron is as large as 9.98 fin. Therefore the hypertriton is barely bound by polarizing the deuteron slightly in order to increase the binding between the deuteron

and the A.

Table 11.8. Partial-wave

decomposition

1

0

2

4

C2

0.99913

0.79 X 10-3

0.6x 10-4

The trial function from the

of the

hypertriton

(11.26) gets higher paxtial-wave

wave

function

contributions

term X1'X2. The

parameters A12 determine the appropriate weights of various partial waves. It is of course possible to solve Eq. (11.24) by expanding f in partial waves: cross

f(X1iX2iXI'X2)

E

"'

A (XI X2) [YI (ill) i

X

YI (F2)] 00

.29)

I=even

Eq. (11.24) reduces to a coupled equation for fI(X1, X2)'s. Refer to Appendix A.5 for a method of evaluating the matrix element with this type of basis functions in the case that A (XI X2) is expanded as Then

7

a

(XlX2)le

combination of Gaussians

"

2 1

-bX2

2.Table 11.9 shows the

energy convergence in the partial waves included in the calculation. fin conformity with Table 11.8 the inclusion of S wave alone is a good

approximation to the hypertriton and bigher paxtial waves give modest contributions to the binding energy. Noncentral forces necessitate the inclusion of higher paxtial waves and the PWE will be

slowly convergent

in

general.

Even in the

case

of

potentials the energy convergence in the PWE in one particula,r Jacobi coordinate set depends on a system and an interaction. To central

examine the contribution of forces

we

tightly

bound than the

higher partial waves

in the

case

of central

example of the triton (nnp), which is more hypertriton. The energy has been calculated

consider another

C11.2 Table IL9.

Convergence

of

partial-wave expansions

Convergence of the hypertriton

energy in the

237

partial-wave

expansion (PWE). The CG indicates the result obtained with the correlated Gaussian of Eq. (11.26). The energy is from the three-particle threshold. The deuteron energy is -2.202 MeV.

CG

PWE

1.. E

(MeV)

by using the

0

2

-2.305

-2.358

wave

-2-378

function of type

(11.29),

where x, is the relative

distance vector between the two neutrons and X2 is the relative coordinate between the proton and the center-of-mass of the neutrons. The

spin-singlet state. Two potentials are used: One is the soft-core Volkov (VI) potential [1451 and the other is the repulsive-core ATS3 potential [1461. Table 11.10 compares the PWE results with other methods, the hyperspherical harmonics (HH) expansion method (see Sect. 5-2) and the CG calculation. The PWE gives fairly fast convergence for the V, potential and the inclusion of S and D waves already produces the energy that is close to the accurate value by the HH method. However, for the ATS3 potential the 6 are not convergence is rather slow and the partial waves of up to I

two neutrons

are

assumed to be in

a

=

sufficient to get the energy which is close to the value calculated with the CG basis (11.26). (The two neutrons are assumed to be in a spin-

singlet state, but, as the ATS3 potential is spin dependent, to allow them to be in a spin-triplet state as well leads to lower energy than the result of Table 11.10. The CG calculation including this possibility 100 dimension, gives -8.765 MeV (the rms radius is 1.67 fin) in K which is in perfect agreement with the energy [170] obtained by the =

Faddeev method

(see

Sect.

5.3).

vergence

explain why the ATS3 potential leads to the than the V, potential. The matrix element for

potential

between the two neutrons vanishes for the functions with

Here

we

slower

con-

the central

values, so the potential is not responsible for the mixingin of different partial waves. The potential between the neutron and the proton, however, induces the I-mixing. To see this, we note that the latter potential has the form V(Iax, + bX21) (for the triton case a 1, but it is extended to a general case.), which is a :E(1/2), b function Of X17 X2 and the angle,& between x, and X2. The potential can be expanded in terms of the multipole operators as follows different I

=

=

Complements

238

Convergence of the triton

Table 11.10. sion

(PWE).

The two neutrons

are

See Table 11.1 for the nucleon-nucleon

V,

energy in the

assumed to be in

partial-wave expanspin-singlet state.

a

potential.

[1451 HH[1691

PVVE

1niax E

(MeV)

ATS3

0

2

4

6

-8.005

-8.390

-8.447

-8.460

-8.4647

[146] CG

PVVE

Imax

E(MeV)

0

2

4

6

-2.948

-6.215

-7.210

-7.484

-7-616

00

V(Iax, +bX21)

=

EV1(XI,X2)P1(COS'6)

(11.30)

1=0

with VI (X1 i

X2)

=21+1 2

7r

fo

V(Iax,

+

bX2 I)PI (COS 6)Sin'0d#-

example, for the Gaussian potential of V(r) (see Eq. (6.53) or Eq. (A.81))

For

VI

Voe-t2T2

we

have

(X1 X2) i

=

where

=

(11-31)

Vo (21 + 1) c(l, ab) il (2 M2 jabjX1X2)

E(I, ab)

=

I for ab >

0, E(I, ab)

=

2 2 2) -g (a 2 xj+b X2,

(- 1)

1

(11.32)

for ab < 0. Since the

Legendre polynomial PI(cosO) is proportional to the tensor product [YI(i-1) x Yj(i2-)joo (see Eq. (6.54)) and has non-vanishing matrix elements between the functions of different partial waves, we find that the various multipole components contained in the potential bring about the mixing of the higher partial waves. The relative strength of the multipoles thus determines the extent to which each partial wave is contained in the solution. For a long-ranged potential (small p) the magnitude Of V1 (X1 X2) is determined by the factor IL21/ (21 1) 11, the soluto contributions main low that so partial waves give only tion. However, this is not the case for a short-ranged potential. The -

7

is, the larger the contribution of thehigher in the extreme case of V(I ax, + bX2 1) E.g., inultipole components. shorter the

potential

range

-

Quark

C11.3

Pauli effect in s-shell A

hypernuclei

239

(fk2/7)3/2 and letting 1L oc in Eq. J(ax, + bX2), by putting Vo (11.32) We get VI(X1, X2) ((21+ 1)/(47))J(Ialxl jbjX2)1(jabjXIX2), ,

=

-

-

which indicates that the

multipole strength is equally strong for arbi-

trary 1. The result of Table 11.10 the fact that the ATS3

repulsive-core part. Clearly the matrix

be understood in this way from contains the strong short-ranged

can

potential

element for the central

potential

between the

neutron and the proton vanishes for the functions of diffrent I values if they are expressed in terms of the different Jacobi coordinate set where

the first coordinate is chosen to the relative coordinate between the neutron and the proton. This consideration leads us to the following ansatz for the solution

(X(I), X(1)) [Y,(X(,)) YJ(X(1)) 100

f

1

1

2

X

2

1

+

X

fl(3) (X (3), (3)) [yJ(X(3))

X

1

+

where

fl(2) (X (2), (2)) [yJ(X(2)) 1

x('), x(') (i 1

=

2

X

X

1

2

1

2

1

1

y1I

(X(2))j 2

Yj(X 2(3))

00

100

(11-33)

1, 2, 3) stands for the ith Jacobi set (see Sect. 2.4).

This type of functions is used in the Faddeev method and the CRCG [26] method. It is known that this expansion converges much faster than the one using one particular Jacobi set, and the inclusion of low

partial waves

is

be sufficient to get accurate solutions (see In contrast to this approach, the CG basis

expected to

also Sect. 4.2.1 and

[30]).

particular Jacobi coordinate but takes account of the contribution of the high partial waves by the cross term 1412XVX2 in the exponent of the trial function. This ensures accurate solutions in the correlated Gaussian approach. It is noted that the calculation of matrix elements with high I values is computer time consuming (see Appendix A-5), whereas in the CG basis no such PWE is employed, which makes it possible to calculate matrix elements very quickly. of

Eq. (11.26)

uses

only

one

Quark Pauli effect in s-shell A hypernuclei 4 3 and 5A Ije are Called Among a few known A hypernuclei AH, 4jA 1, AIIe, s-shell hypernuclei because in the simplest version of the shell model 0 all the constituents can reside in an s orbit. By applying the L 11-3

-

=

240

Complements

correlated Gaussians of

Eq. (7.3),

of s-shell A

in order to reveal the

hypernuclei quark substructure of baryons of

in

we

calculate the

resolving

the

binding energies significant role of the long-standing problem

'He. Since the

pioneering work of [1711, the S-shell A hypernuclei have intriguing problems, among others, the anomalously small binding of 5AHe. According to a recent survey of hypernu5 clear physics [1721, "The anomalously small binding of AHe remains model calculations an enigma. Simple based upon AN potentials, parametrized to account for the low-energy AN scattering data and the binding energy of the A 3, 4 A-hypernuclei, overbindS A5He by offered several

=

2-3 MeV."

The trial function is

given as

a

combination of the correlated Gaus-

sians:

CkAjFAk (X)XkJM?7kTMTli

TfJMTMT

(11.34)

k

where the operator A

antisymmetrizes the nucleon coordinates, XkjjU (Since L 0, the spin S is equal to the total angular momentum J), and 77kTMT is the isospin function. The spin and isospin functions are obtained by successive couplings, for examPle, XkJM= X(S12SI23 )JM [[[Xl/2 X XI/21SI2 X X1/2JSI23-IJTM with k representing a set of the intermediate spins S12, S1237 The optimal set was chosen for each matrix Ak. The matrix Ak containing is the

spin function

=

:::--:

...

....

nonlinear parameters

was

selected

by

the SVM.

The NEnnesota potential [1471 with u I was used for the NN interaction. The MA potential is the same as was used in the previous Complement. Table 11.11 lists the results of the calculation. The calculation reproduces the data well except for the case Of AHe, for which the theory overestimates the binding energy by about 1.9 MeV, =

consistent with what is mentioned above. Another is that

4 He A

is

bound than

4 H. A

thing to be noticed

strongly introducing a charge-dependent component as the IVA interaction, because then 4AHe would be less tightly bound because of the Coulomb repulsion. We have so far treated a baryon as a structureless particle and distinguished A from N. What happens if we take their quaxk substructure into consideration? Recently it has been shown in [173] that the anomalous binding problem of 5A He can be, at least partly, resolved more

It would be difficult to

understand this without

by considering

the

quark substructure

of the

baryons.

C11.3

Quark Pauli effect

in s-shell A

241

hypernuclei

Binding energies (in units of MeV) of s-shell hypernuclei. The separation energy BA of the hypernucleus AAX is defined by the difference of the binding energies, B(-A'1X)-B(-'1-1X). Table 11.1-1.

A

3

AH

A411

4AHe

5 He A

B(AX) A B(`1-1X)

2.38

10.62

9.91

34.93

2.20

8.38

7.71

29.95

BA(Cal.) BA(Exp.)

0.18

2.23

2.20

4.98

0.130.05

2.040.04

2.390.03

3.120.02

Let

us assume

for the sake of simplicity that

baryon is (u, d, d), A a

a

coinpos-

(u, d, s), (u, u, d), n particle of three quarks, p well. harmonic-oscUlator the in orbit in the Os and each quark moves with size parameter b. The spatial part of the three-quark baxyon is described by the function ite

=

=

OB

-`

(7rb2)

1

-1 4

exp

Z3

b2

( '3

(_ (P2 P2 P2)) (_ _b 2) O(int) 2b2

1

+

2

+

3

3

exp

-

where pi is the

=

2rI

(11.35)

B

quark's position vector,

rl

=

(P1

+ P2 +

P30

is the

is the spatial part of the intrinsic baryon's position vector, and 0(int) B of the function wave baryon depending on p, P27 (PI + P2)/2 P3* The value of b can be estimated to be about 0.86 fin by requiring that the function (11.35) reproduce the charge radius of the proton [1741. When the spatial part of the two-baryon wave function is described we interpret it as with the configuration of expf -3/(2b2)(r21 + r2)1, 2 the Os in all six orbit, exp(-p 2/(2b 2)), quarks move indicating that of the common harmonic-oscillator well. with size parameter b. By increasing the number of baryons, we thus expect that the manybaxyon wave function may receive a special constraint arising from the quark Pauli principle that any single-particle orbit can accommodate at most six quarks (three colors and up-down spins) for each flavor. It is easy to see that we have no apparent quark Pauli-forbidden 4 hypernuclei. However, this is not the case for states up to A 5 5He: Four nucleons of A He, when they are on top of one another, A have already six u-quarks and six d-quarks in the Os orbit, so neither u nor d quark of A can take the same Os orbit. This leads us to the conclusion that the five baryons cannot take a configuration of -

=

-

242

Complements

exp(-3/(2b 2) 1:5i=1_ r i2) forbidden state for

rated,

is

.

To be

5AHe,

more

specific, the (normalized) Paulibeing sepa-

with its center-of-mass motion

given by 5

TfPF (X)

=

JV

'(7b2)-3eXP(_ 4

-

3

3

_b2 Dr'

X5)2

(11.36)

i=1

where X5 is the center-of-mass coordinate of the five baryons. The normalization constant is given by JV (4M2 + M2)/(4MN + MA)2' =

N

A

where MN is the mass of N. Other Pauli-forbidden states sibly exist, but this is the simplest and most evident one. The solution TI obtained above for 5He A

Pauli-forbidden component of Eq. quence is very

was

might

pos-

found to contain the

(11.36) by only 0.44:'YD, but its conse-

If this Pauli-forbidden component is simply subtracted from the wave function Tf, the BA value would have been

from 4.98 MeV to 2.74

changed of

A5He!

The reduction is

pectation may be

significant:

a

principle

MeV,

anomalously

small

binding

because the reduction in the

calculation of the so-called variation

6.1),

no

due to the fact that the energy exvalue in TfF(x) is very large, i.e., 513.6 MeV. However, this premature conclusion from the viewpoint of the variational

mainly

binding energy is based on a before projection type (see Sect.

that

is, the variation has been done before the elimination of the Pauli-forbidden component is made from the trial function. To calculate the

binding energy more precisely by taldng into acquark effect, we have repeated the calculation by replacing the correlated Gaussian in Eq. (11.34) with the one that 'has count the

no

Pauli

Pauli-forbidden component:

FAk (X)

11.4 The

FAA: (X)

C nucleus

-

TfPF (X) (TfPF (X) IFAI, (X))

-

(11.37)

system of three alpha-particles example application of nonlocal potentials, we take up simple model for the 12 C nucleus, the 3a model. In this model 12C

As a

12

=

an

of the

as a

C11.4 The

12C

nucleus

as a

system of three alpha-particles

243

5

>4

3

Exp.

Pq

2

0.6

0.4

0.2

0.0

b

Fig.

[fml

separation energy BA of 5H A three-quark baryons

11.4. The A

parameter b of

containing

1.2

1.0

0.8

six protons and six neutrons is

as

a

function of the size

approximatedas

bosonic

a

system of three alpha-particles. The physical reason behind this picture is in the fact that the alpha-particle is a strongly bound, very stable system compared to light neighboring nuclei. One needs an energy of about 20 MeV to excite the of the

alpha-particle.

Because of this

nuclei tend to form

unique

consist-

feature, light subsystem ing of two protons and two neutrons, which is called an alpha-cluster. The alpha-cluster would never be identical to the alpha-particle but it may happen that a model descriptioii assun-Ang such subsystems can explain many properties of the light nuclei [60, 175, 59]. To calculate the binding energy of 12C in the 3a model, one needs to know the potential between two alpha-paxticles. It is hard to derive a potential which acts between composite particles through the underlying interactions of the particles composing the composite particles. Thus we use a phenomenological potential which successfully reproduces the alpha-alpha scattering phase shifts. The one employed here is an I-independent local potential consisting of both the nuclear some

paxt of Gaussian form and the Coulomb part

V(r)

-Vo

e

_P,

[1761:

4e2

2 =

a

erf (,3r),

+ r

(11-38)

244

Complements

where VO

122.6225

=

MeV, p 0.22:ftn-2, and scattering data very well

0.75 fin-'.

=

fits the

this

Though

to about Em

30 potential MeV and reproduces the 0+ resonance at 92 keV quite well, we have to note that it predicts "redundant bound states", two (-72.625 and

-25.617

I

=

2

in the I

MeV)

state, these bound states ftom the

0

=

Since the two

wave.

wave

and

one

(-21.999 MeV)

known to form

in the

bound

alpha-paxticles considered spurious and must be excluded are

no

axe

space. The existence of

configuration

=

system of two nuclei is due understood in the

to the Pauli

spurious

principle

and

states for

can

be

a

easily

version of the nuclear shell model. This is

simplest orthogonality condition model [1771 which succeeded to give a foundation to the deep local potential of type (11.38) from the microscopic theory of scattering between composite particles. Let us denote the spurious states as 0, 1 for I (r), (n 0 for I 0, and n 2). We require that the wave function TI, for the 3a system be free from the spurious components in the alpha-alpha pairs, that is, the basis of the

=

=

=

( Pnim(ri

-

rAff)

=

(11.39)

0-

Here ri is the position vector of ith alpha-particle. Unless this condition is imposed, the ground-state energy with the potential (11.38)

strongly overbound because

would be

the

alpha-clusters,

as

bosons,

would occupy the lowest possible states. An alternative, convenient approach to eliminate reasonably well the spurious components is to use

the nonlocal

Fini

1M ==

potential of projection operator type

I

(ri

rj)) (W,,,M (ri

-

and include it in the Hamilto-nian

-

as a

kind of

N

I

=

T

-

Vij(lri-rjl)+A

Here A is

a

wave

positive

E EI'i'!

(11.41)

j>i=l n1m

j>i=l

that if the

"pseudo potential" [178] N

E

Tn, +

(11.40)

rj) 1,

constant chosen to be very

large. The idea

is

function contains the spurious components, then the energy would be comparatively high. Therefore, the variational lowest solution would approach a state that has a negligible overlap with the

spurious components. The spurious bound

state

lar

O,am (r)

Cae- 2 a

can

be well

approximated

in the form

2

Y1. (r)

(11.42)

CIIA The

12

Then the nonlocal

C nucleus

potential

as a

245

system of three alpha-particles

summed

over m

takes the form

_Vnlra

f

ij

M

21+1

(rr') -47r

R

(cosv) E ca*ca, e-la 2

r2_ 1 af rf2

(11.43)

aa,

where V is the

between

angle

r

and

r.

The trial function for the

system was chosen as a linear combination of the correlated Gaussians, FA(x), of Sect. 7.2. The matrix element of the nonlocal potential (11.43) in this basis can be calculated with the use of Eq. (7.46). 3a

high sensitivity of the energy on A calls for numerical calculations with a high accuracy in order for the pseudo potential to play the role of the Pauli projector. It was found [1791 that the pro0 and 2 do not jection effect is so strong that the partial waves 1 The

=

contain bound states, and a contribution of more than 95 % to the ground-state energy is due to the partial wave I 4. Table 11.12 lists =

the

energies

of the

ground

state and the excited states obtained in

a

[1801 using the basis function of Eq. (11.33). h (X1 X2) is expanded as combinations of Gaussians 2 The calculation does not reproduce the experix11 x12 exp(-ax 1 _OX2) 2 mental energies very well. In [1801 the energies of the 2+1 and 41+ states

variational calculation The radial part

are

also

given. They

are

-3.77 and -2.25

MeV, respectively, which

compared to the experimental energies of -2.84 and 6.80 MeV. Here the discrepancy between theory and experiment is more serious: state is lower than that of the 0+1 state and the The energy of the 2+ , energy of the 4+1 state is much lower than the experimental energy. are

Note that there is

no

Pauli-forbidden state in the 1

makes the contribution of the

high partial

> 4 waves,

waves too much

which

important.

This calculation suggests that the 3a model with the local aa potential has only limited success and is not very realistic to reproduce the experimental energy spectra. This doe not, however, exclude the

Table 11.12. Energies of the 0+ states of 12C calculated in the 3a model [180]. The energy is measured from the threshold of the 3a breakup.

0+ 2

0+ 3

-3.38

-1.43

3.70

-7.27

0.38

3.03

0+ 1

(MeV) Exp. (MeV) Cal.

246

Complements

a

+

8Be,

a (

and

'Be(a,-y)12c.

Appendix

Matrix elements for

Gaussians

general

The matrix element for the correlated Gaussian with

arbitrary physically important potentials including central, tensor and spin-orbit components. A simple and straightforward method is presented to calculate the matrix element for the general correlated Gaussian-type geminals.

angular

momentum is obtained in

a

closed form for most

A.1 Correlated Gaussians We start with

Eq. (7.2)

to evaluate the matrix element for

a general generating functions g is given perform the operations prescribed in Eq.

The matrix element between the

case.

in Table 7.1 and

one

has to

(7.2). A.1.1

The

Overlap

overlap

of the basis functions

matrix element

can

be obtained

through

(fK" LM (u, A", X) 1 fKLM (u, A, x)) I

BKLBK-'L

ff

_ d9de'YLm(i;_)YLm(e')

d2K+L+2K+L

dA2K+LdAI2K'+L

3

X

detB

exp

[q A2 + q"A/2 + PAA/e. er]

where

Y. Suzuki and K. Varga: LNPm 54, pp. 247 - 298, 1998 © Springer-Verlag Berlin Heidelberg 1998

\,=0

,

(A. 1)

Appendix

248

B=A+A',

q=

2

fiB-lu,

B-lu ,

q

2

p

=; B-lu.

(A.2) To

perform

the

operation prescribed

Eq. (A.1),

in

we use

the

ex-

pansion

[qA2 + q, A/2 + pAA/ e. el]

exp

CO

00

CO

E 1: E H(n, q).ff(i , q) H(m, P) Vn+m y2n+m

fn

n=O n'=O m=O

(A-3) where

H(n, x)

is introduced to Xn

10

H(n, x)

for

n!

simplify the

notation and defined

non-negative integer

n

by

(A.4)

otherwise.

Differentiating with respect to A and Y, followed by A 0, 2K + L and gives non-vanishing contribution only when 2n + m 2K' + L, while the integration over the angles of e and e' 2n + m becomes nonzero if m is equal to L + 2k with non-negative integer k (see Eq. (6.18)): =

=

if

d iYLM(e-)yLM(,

di

1

j)*(e.eI)2k+L

K k and n Rewriting n overlap matrix element =

-

=

K'

-

k,

=

we

BI.-L

(A.5)

obtain the result for the

(fKIILM(UI, A', X) IfKLM(u, A, x)) 3

(2K+L)!(2K'+L)i

(27)N-1-

BKLBKIL

detB

2

min(K,K') X

E

H(K-k,q)H(K-k,q)H(L+2k,p)BkL- (A.6)

k=O

The B,,I value is given in Eq. (6.9). Note that the values of K and K' usually be chosen to be small. in practical cases, and then the sum

can

over

of K

k is limited to =

K'

=

just

a

few terms. In

0 the above result

particular, simplifies to

for the

special

case

A. 1 Correlated Gaussians

249

(ALM(Uli A i X) IfOLM(Ui A X)) 3

(2L + 1)!!

(2v) N_I

(

4v

detB

2

)

L

(A.7)

P

A.1.2 Kinetic energy

The kinetic energy with the center-of-mass kinetic energy subtracted is given in Eqs. (2.10) and (2.11). It is simply written as FrAn-/2. The matrix element of the kinetic energy is then

Table 7.1

easily obtained by using

as

I

(fK"LM(UIjXjX)j ?rA7rjfKLM(UjAjX)) h2

(2r) N-I

2BKLBKIL

detB

(

d2K+L+2K+L

[R

X

dA2K+LdA/2K'+L

X

exp

3 2

+

if

de-- do

pA2

+

YLm (&) YLM (4 )

p/A/2

+

QAA'e-.e-f

[qA2 + q' A/2 + PAAte.e/

(A.8)

where R

M(AB-'A!A),

=

P'=

P

=

-i B-'AAAB-lu ,

-i!B-1A!AA!B-'u, Q

=

2

The matrix element of the kinetic energy manipulation similar to the overlap case:

B-'AAXB-lu. can

be obtained

I

rA7rjfKLM(u, A, x))

(fKfLM(Uf7A!jX)j 2

3

(2r)N-1

h2(2K+L)!(2K+L)!

x

detB

BKLBK"L

2

E f RH(K

k, q)H(K'

-

2

-

k, q)H(L + 2k, p)

k

+PH(K

-

k

-

1, q)H(K'

-

k, q')H(L + 2k, p)

(A.9) by using

a

250

Appendix

+P'H(K

k, q)H(K'

-

-

k

-

1, q)H(L -IF 2k, p)

+QH(K-k,q)H(K'-k,q')H(L+2k-l,p)lBkLThe

case

K'

with K

=

0 reduces to

a

(A.10)

simple result

very

(ALM(U17A x) I --iAw I fOLM (u, A, x)) 2 ,

h? 2

A.1.3 Next

(2,x)'V-1

(2L + 1)!! (R+LQp- )-

detB

4-x

3 2

)

L

(A.11)

P

Two-body interactions

we

derive the matrix element for the interaction of Eqs.

(2.3)

and

(11.1). To evaluate the matrix element of the operator expressed as a tensor product, it is convenient to make use of the famous WignerEckart theorem

spherical

[70, 71, 721, which states that a matrix element of a operator 0.-, between states with angular momenta

tensor

JM and XIW

coefficient and

be

can a

expressed

as

product of

a

reduced matrix element which is

z-components of the

(J'M'JO-AIJM)

angular

a

Clebsch-Gordan

independent of the

momenta:

(JMrILJYM-) =

,V2J'

V 110. 11 J).

(A.12)

+ I

Here the reduced matrix element is barred matrix element. The factor

expressed by the so-called double-

I/V -2-Y+I is factored out because

then the reduced matrix element is

symmetric

to the bra and ket

interchange

IEV 110. 11 X) provided of

OKIL

is

=

(-I)J+r.-J,(y 110. 11 J),

(A-13)

that the matrix element is real and the Hermitian

(0'1')

t

=

E(- 1)

"L

Or,, -i-L

with

a

phase

factor

E(E2

conjugate =

1).

By applying the Wigner-Eckart theorem we can express the matrix element for the orbital and spin angular momentum coupled wave function

as

follows:

(Tf(LI SI) JM IV(I'ri

-rj 1)

(Or ij (space) 0,,ij (spin)) ITf(LS) JM)

U(LnJS; L'S) V,f(2L' + 1) (2S + 1)

-

A.1 Correlated Gaussians

(L' 11 V(Iri

x

rj J)0,,jj (space)

-

251

11 L) (S' 11 0,,jj (spin) 11 S). (A.14)

potential V(r) is assumed to be a function of r only. Eq. (A.14) and its extension to a general coupled tensor operator is given in Exercise A.I. The reduced matrix element of the spatial part is obtained through Here the form factor of the

The derivation of

(LMn1ijL'M') (L' II V(I ri v/2--L'+I (L'IWIV(Iri

=

jV(r)(LM'jJ(rj case

uncoupled by

where

wave

-rj

(_1)r. 2S'

one uses

-

I I L)

-

r)O,,,,,j (space) ILM)dr.

the orbital and spin matrix element

(A.15)

angular momentum

(A.14)

can

be obtained

(0,,,j (space) 0,j (spin)) lTf(LS)JM)

ri 1)

-

U(LKJS'; LIS)

+ I

2S+1

x

-rj

function, the

R(L"S")JM IV(Iri

rj 1) 0,,i, (space)

(space) ILM)

=

In the

-

(LMLts1-tjLIML')(SMSrvjS,MS)

(TfL,MLS,ms, IV(Iri -rj J)0,st,,j (space)Oc,jj (spin jTfLmLsms) (A.16)

Since the spin matrix element is easily calculated as will be shown in Appendix AA, we will focus on the spatial matrix element and evaluate it for the most important components of the nuclear potential, that is, central, tensor and spin-orbit components.

(i) central

and tensor interactions

The operator

Or-A,j (space)

can

be I for the central

potential

and

Y2,,(r-i---r-j)

for the tensor operator. See Eq. (11.7). Thus both the central and tensor components can be treated by assuming the form

---rj) for 0,,,,,3. (space). Expressing ri

of Y,,,,, (,r-i

(N 7.1,

-

1)

we

x

1 column matrix

-

rj

as w (ij) x

Oj) defined iii Eq. (2.13)

and

with the

using Table

obtain

(fK'L'M'(UI74 x)IS(ri

-

rj

-

r)Y,,j,(rj

-

rj) IfKLM(U7 -47 X))

Appendix

252

'::::-

6)(fKLM(UIi W 7x)IJ(W(ij)X-r)jfKLM(u,A,x))

Yrg(

(27r)N-2C

1

2

1

e-fc7'Y-"(i )BKLBKL' X

if

de^- d,

detB

3 2

)

d 2K+L+2K'+L'

iYjLM(e,-) YJL, M,

dA2K+LdAI2K'+L'

XeXp[q,X2+ A/2+ Aye.e/+7Ae.,r+,Y/,XIe/.,r] (A-17) where C

w(ij)B-lw (ij)

c

I

^/2

q=q-

712

q'-

2c

w(ij) B-1u, =P-

2c

cw(ij)B-1U',

7

1'7YI.

(A.18)

C

All of these quantities

depend on i and j but we omit the labels i and j to simplify notations. The integration over the angles of e and e' can be performed by expanding exp (pAVe- e' + -/Ae- r + -l'.Ve,- r) in -

power series and

-

using the relation

(e.e )nj(e.T)n2(eI.,r)n3 n2 +n3

Lel=l

njn2n3

RL Lfn

[[YjL( )

X

Y

X

(A.19)

Y. 00

LL'r.

with Rnjn2n3 2 LIts

=

(_I)nl+n2+n3

Bnl-LI7 Bn2-12 12 Bn,3 -13 2

'1

2

2

3

111213

E(2L+:1:1 ) (2

V

r.

+

212+1

1)

C(1112; L)C(1113; L)C(1213; K)

U(IIIILK; L'12).

(A.20)

See Exercise A.2 for the derivation of this relation. In the

defining

I or 0, and 12 equation for R the sum over 11 is limited to ni, ni 2, and 13 have similar ranges, respectively. Possible values of L, L", and r, -

...'

A.1 Correlated Gaussians

for

a

given set of values of ni, n2, and

n3

limited

axe

253

by the conditions

that L takes the values nj +n2, nj +n2 2, ..., I or 0, and L' and r, take similar values given by ni, n3 and n2, n3, respectively. In addition, the -

is restricted to

sum over

L, L,

for

values of

given

and n2 + n3

-

would vanish.

K

r.

even

values of L + L+ K.

Conversely,

L, L', and K, all of the nj + n2 L, nj + n3 L, have to be non-negative and even, otherwise Rnin2n3 -

-

LL'r.

R has the symmetry: The reduced matrix element becomes

Clearly

(fK'L'(UIi -4 i X) 11 V(17'i

-

ri Dyt#

njn2n3

RLLII,,

pnjn3n2 "L'Ln

i -rj) 11 fKL (u, A, x)) 'R

Lf

(2K + L)! (2K'

+

L') 1

BKLBKILI

E

x

(

(27) N-2 detB

C.)2

H(ni, #)H(n2, -y)H(n3, 71) I(n2+n3+2,c)RnL,-n2n3 LIn

n,n2n3

2K + L

-

XH

nj

-

2K+L'-ni-n3

n2

2

2

(A.21) where the

I is defined in

Eq. (7. 10) potential for different pairs of particles be calculated with the above formula by changing only 01) in

integral

The matrix element of the can

Eq. (A. 18). We note

some

useful

applications

of

Eq. (A.21). For example,

calculate the matrix element of I ri-rj I' simply by putting r' and K 0. The two-paxticle correlation function can

one

V(r)

=

(fK-'Ll (u, A', x)

J (I ri

-

rj

a) Y,, (ri

-

rj)

fKL (u, A, x))

(A.22) easily calculated by taking J(r a) for V(r). K' We note again that the formula (A.21) simplifies for K 0, that is, the triple sum reduces to a single sum over, say ni (nl_ 0, min( L, L', (L + L' r,)/2)) and n2 and n3 have to satisfy L and nj + n3 L, respectively. In addition, in this nj + n2 njn2n3 calculated is R case simply by a term with 11 special nj, 12 n3 alone in Eq. (A.20). This simplicity will be used to obtain n2, 13 the matrix element of a density multipole operator. See Complement can

also be

-

=

=

=

-

=

=

=

=

A.2 for the details.

254

Appendix

(ii)spin-orbit The operator

angular

interaction

0,,,,,, (space)

momentum

((ri

rj)

-

1-

x

2h

and

and

(2.14)

trix element in Table 7.1 into

(fK"L"M"(Ufi Al7X)jV(jT'i

substituting

pj))

See

,.

x

and

Eq. (11. 9). -r,

with the

we

the

corresponding

ma-

i

obt

I'jj)1jzjjjfKLM(u, A, x)) (27)N-2

.1 Cr2

drV(r)e-2

-

is the orbital

1,

Eq. (7.2),

-

(pi

in terms of

x

Eqs. (2.13)

of

=

spin-orbit potential

Fij)x W)7r)

Expressing 1,_,,j use

1,1i,

for the

3 2

C) I

detB

BKLBK'Ll

d2K+L+2K'+L'

dA2K+LdA/2K'+LI q

x

exp

X

ifn*

+

X

qf A/2

r)t,

-

+

PAy e. ef + yXe.,r + -Y/Ale/. -

q'Af (e,

X

(A.23)

r),,

with 77

=

(MXB-lu,

Note that to derive

an

arbitrary

=

Eq. (A.23)

V(r) e-c('-a)2 (r for

q'

vector

x

a

a)dr

(MAB-luf. use

=

(A.24)

is made of the relation

(A.25)

0

provided V(r)

is

a

function of

r.

See

Eq.

(A-163). Before

performing the operation prescribed

that the matrix element vanishes in the has

parity

(_I)L

and because the

case

Eq. (A.23), we note 0 L. Because fKLM

in

of L

spin-orbit potential

does not

change

A. 1 Correlated Gaussians

parity, IL

-

L'I

has to be

even.

On the other

hand,

255

the tensorial char-

spin-orbit potential imposes the condition IL LI :5 1. Both the conditions are met only when L is equal to L'. This special result is entirely due to the unique feature Of fKLM and does not always hold for general wave functions. Combining Eq. (A.19) and the relation acter of the

i

fqX(e

-

r) 0

X

4vf2--x 3

-

77W (e'

rjqA[Yj(ii)

X

x

r)

Yj(i )Jj, -,qA[Yj(( )

x

YI(,P)JI, (A.26)

yields

the reduced matrix element

(fK,ILI (Ul A! X) I I V(I'ri I

I

as

-rj 1) Iij

I I fKL (u, A, x)) '3

4 V2--x

JLLI (-1)

3

x

E

q

L

(2K + L)!(2K' + L)!.

(27r)

( N-2C.)2 detB

BKLBKIL

l(n2+n3+3,c)H(nl,p)H(n2,,y)H(n3,-y')

n,n2n3

2K+L-nl-n2-1 H

xH 2

(2K'+

L

-

nj

-

n3,,,)

2

n., n2 ns

C(AI; L)U(LAII; 1L)RAL1

x

A

I(n2+n3+3,c)H(nj,#)H(n2, -y) H(n3 7f)

+77'

,

njn2n3

H

x

(

2K+L-nl 2

-n2

q)H(

2K+L-nj

njn2n3

C(AI; L)U(LA11; 1L)RLAI

-n3

-

1

2

(A.27)

straightforward and easy to follow. As a simple check of the above formula, the matrix element of the orbital angular momentum is calculated in Exercise A.3. It is again possible, however, to get a simpler formula by performing the'P integration first, as was done in Complement A. 1. This task is reserved for Exercise A.4. The above derivation is

256

Appendix

A.1.4

Density multipole operators

The matrix element of

density multipole operator plays a substantial role in investigating the properties of a system, e.g. the density, the deformation, the electromagnetic transition rates and the electron scattering form factors. The basic element of the Multipole operator a

takes the form

0,,,L, (space)

:---

f (Iri

xm

-

I)YI,

(A.28)

Note that the argument of the

density multipole operator is not ri but is correctly taken as ri xN, which is the single-particle coordinate measured from the center-of-mass coordinate. Comparison of Eqs. (2.12) and (2.13) immediately suggests that the matrix element of the density multipole operator ought to be calculated in exactly the same manner as that of the two-body potential. In fact the reduced -

matrix element

(fK"L-'(U/7 X7 X) 11 f (ITi

-

XNI)yn(Tii

-

N)

fKL (u, A, x))

XN

(A.29) be calculated

can

replacements

of

by Oj)

the --+

same

formula

as

0) inEq. (A.18)

Eq. (A.21) and of

with the trivial

V(r)

--+

f (r)

in

Eq.

(7.10). Just

as

the matrix element for the

lated from that of relation function

As

we

J(ri

can

xN

-

-

r),

and ri

be calcu-

the matrix element for the

also be derived ftom. that of

J(ri

-

rj

-

-

-

reduced to the

are

r)jfKLM(u,A,x)).

in fact obtained in the derivation

one

(fKfL'M" (U , X7 X) IJ(17VX (2K + L)! (2K'

+

BKLBK'L'

-

L)!

following Eq. (A.17),

r) IfKLM(u, A, x)) (2T,

)N-2C)

32

detB

E(LMr.M -MjLM)Y,,m, -m(i )* M

of type

This matrix element

the fi-nal result:

x

r).

-

(fK'L'Mf(U'jA!jx)jJ(iv-x give

cor-

-

already noted in the above derivations, both of ri xN rj are expressible in terms of the relative coordinates x as iv- being an appropriate 1 x (N 1) row matrix. There-

fore all of these matrix elements

we

can

have

Cvx with

was

density operator

L'

-1) -e -v/-2Ll + I

2

so

that

A.2 Correlated Gaussians with different coordinate sets

E

X

257

rn2+n3 Rnin2n3 H(nl, P) H(n2, -y) H(n8, -y') LLIn

nin2n3

2K+L X

H

-nI -n2

2K' + L'

-

H

2

n,

-

n3

2

(A.30) 7/,

given in exactly the same manner as in Eq. (A.18) with w(W being replaced by w. Here, r, takes the values

where c, 7,

p

are

L+L', L+L'-2,..., IL-L'I,

and it is of course restricted

by IAF-MI :!

The above matrix element becomes very simple for the special case K' of K 0 as was noticed in the previous subsection. Since the is.

=

=

applications, we show in Complement A.2 simplified to just a double sum.

matrix element has useful

that

Eq. (A.30)

can

be

A.2 Correlated Gaussians with different coordinate sets As the correlated Gaussians treated in the previous section have a very simple transformation property implied by Eq. (6.29), we as-

they are all expressed by a particular set of the relative coordinates x. However, the correlated Gaussians with the angular function OLM(X) given by Eq. (6.3) do not have such a nice property. Moreover, the use of different sets of the relative coordinates for these correlated Gaussians leads in general to a faster convergence because they allow us the possibility of describing naturally different types of correlations and asymptotics. The lineax transformation of the coordinate sets, however, leads to a formidable task even for a system of only four particles, because the function OLM(X) shows no simple transformation rule. See Appendix A.5 where the matrix elements for a three-body system are explicitly evaluated by transforming the corsumed that

related Gaussians from

one

Jacobi coordinate set to another. The aim

of this section is to outline ments for are

we

a

method of

calculating

the matrix ele-

the correlated Gaussians which

N-body system using expressed by different sets of the coordinates. By making use of Eq. (6.22) to generate the correlated Gaussian, have to evaluate the following matrix element for the operator 0: an

N-1

exp,

2

x-fXx)

11 Yij, j, (x ) j=1

Appendix

258

N-1

-1:Z.Ax)

1

0 exp

x

N-1

Yli.i (xi)

2

Climi,9ai

N

ali-Mi

01i

-

1

01j,i +Mi'

(-')Mj 01j,

3

C11 -mlj aal - ar'1j'+mi' j j j

97i j=1

(A.31)

(g(a'Jt';A!,x')J0Jg(aJt;A,x))

x

ri=O,-r =O 3

(-1)'YI-,,,(xi) to identity (Yl,,,(xi))* take care of the complex conjugation in the bra side. Note that the vector ti is defined by 2, i(l + i 2), -2-Fi) and likewise t!j by Here

(1

is made of the

use

T,

/2' i(I + T/2), -2,Tj j

complex conjugated.

transformation T trix element

x'

as

(A.31)

of g in the bra side should Assume that x' is related to x by a linear

The vector

j

not be

=

=

tj'

Tx. With the

between two

g's which

different sets of relative coordinates

Eq. (6.28) expressed in

of

use are

the

ma-

terms of

be reduced to

can

(g(a'lt'; X, x')J0Jg(aJt;A, x))

(g(Ta'lt';i XTx)101g(alt;A,x)), and

can

(A-32)

be obtained from Table 7.1 for most operators. 1, the matrix element

(A.32) takes, where v alt+ except for a trivial constant factor, the form e2 B' is matrix the and x given by (A+ TXT) (N 1) (N 1) Ta'It' For the unit operator 0

=

-IbB'V

=

,

-

-

To

simplify the

SN-1,

a.el

=

aNtIV

=

we

SN,

---,

rename

alt,

afN-,eN-l

=

expressed by a (2N 2) by 9Bs, where B is expressed in

6B'v

Then

notation

matrix B

can

be

-

aN-1tN-1 a2N-2t2N-2 82N-2-

-=

si,

x

(2N

-.-,

-

2) symmetric

terms of B' and T

as

follows

B

=

Thus the

(

B'

TB'

Bi TB'i

(A.33)

operation prescribed

in

Eq. (A.31)

can

be reduced to the

form N-

Oi",`

exp,

(2IBs

+ ibs

))

(A.34) .1=0'---'12M-2=0, 1=0,---,'2N-2=0

A.2 Correlated Gaussians with different coordinate sets

259

with

(A.35)

i9ail 0-Til-m Here the factor iv-s is included because it is needed in the

case

of the

potential energy matrix elements. See Table 7.1. It is worthwhile noting that the present formulation leads to a unified prescription of Eq. (A.34), which is independent of the choice of the relative coordinate sets but requires only a very simple calculation of the matrix B. It would be extremely tedious if one were to try to rewrite the anguN 1 lar function of fL'=I Yj . (x'.) in terms of those angular functions 3 conforming to the coordinates x. Using Leibniz's formula we can express Eq. (A.34) as 3

2

2

T

3

=1

Aj! (Ij

'XiAi

-

Ai)! (Ai

(1i Mj)! (1i

-

-

-

Mi)! mi

-

Ai

+

Ai)!

2N-2

Oj"

X

exp

(2 Os) -ri=O

2N-2

ai

X

ie,

(A.36) aj=O -ri=O

The last factor is

easily evaluated by using Eq. (6.58):

2N-2

11

ali-'Xi'mi-Ai e-vs i Ui=O -ri=O 2N-2

(A-37)

CIi-'XiMi-/-tiY1i-)LiMi-Ai(Wi)-

Possible values of Ai and [ii are determined by the conditions that O
vanish. Because of condition that Ai

-

assures

do not

that the coefficients

a special form of si-sj mentioned pi < 2Aj has also to be met.

below,

another

remaining factor, we note that ABs is quadratic both in the ai's and -ri's because of si sj -2aiaj (ri -r.j) 2. (S ince, for each aj, -ri appears at most in quadratic power, the number of To evaluate the

-

=

-

260

Appendix

differentiation with respect to -ri cannot exceed two times the number of differentiation with respect to aj, that is, /Xi pi :! 2Aj.) Therefore, -

.!Bs 2

when

e

these

are

contributes Thus

we

expanded in power series in both ai's and -Fi's, and when zero after the differentiation, only the term (.IgBs)Q 2

is

set to

2N-2

provided that Ej=j

2Q and

Ai

2M-2

2Q.

i=1

(-2)Q

19Bs a,\"/L'exp i

(2

Q!

Cti=O -ri=O

Q

2N-2

EBjjajaj(Tj-T.j)2

X

i=1

To have

1:2N-2 (Ai ILi)

have

(A-38)

i<j

aj=O -ri=o

non-vanishing contributions,

each of

Q

terms must be dif-

ferentiated with respect to aj, aj, and either twice with respect to 7i or -Fj, or once each with respect to both 7-i and -rj. This operation

yields 2Bij,

where the miniis

to -ri and -Fj. This

respect

sip

sign comes from the differentiation with is

denotedEij.

Therefore

we

obtain

2N-2

a,"' '14 exp

(2sBs)

ai=o -ri=O

(-4)Q Q! Q

(A-39)

Ejj, Bi,j,

x k=1

'k<jk

where the

extends

all the

possible combinations distributing the given multiple differentiation into pairs of differentiations. In fact the operation prescribed in Eq. (A.38) can be done easily by using the software Mathematica [1841. The case of a three-particle system is given in Co mplement A .3. sum

over

The matrix element for the kinetic energy can be obtained similarly. In fact the matrix element (A.32) for the kinetic energy takes the form relation

(9Cs)e12'BS,

but this

can

be dealt with

easily. Using

the

A.2 Correlated Gaussians with different coordinate sets

(Ws) exp

d

1Ms

(2 )

2

dp

( 19 (B +pC) s)

exp

261

(A.40)

2

P=O IgBs

(112N-2 aj " "Ws ing

one

of the

)

e2

j=1

Bi,,j,,'s

Eq. (A.39)

in

be obtained

can

by simply replac-

ai=O,ti=O

with

Ci,j,.

The

potential energy matrix element for the spin-orbit interaction requires a slight modification. Noting that the general form of the matrix element (A.32) for this case can be expressed as + ivis) (see (Sk)yeXP (19B.9 2

(2IMs

(Sk)jzeXP

7.1),

Table

+ iv-s

( -1)"

we

make

use

exp

ly(Wk)-M

(OWk)jj (21ABs ) exp

where the a,

spherical components a,,

- 2=(a.,

=

+

iay),

ical components a

( aa) .1

V-2

1 =

-72=

1

(

(

ao

of

aa

a

+i

-9a.

=

Da,

-67a--,

'9

aal

-!9Bs+fvs

e2

)ai=O,-ri=07

Eq. (A.37) with

lated ,r

by -

the

can

.

be obtained

a

-

(A.41) are

iay),

(a

defined

and the

-5a I o

=

Da-,

by spher-

given by

are

la

a

7Eo

I

"&a )-1

=

2N-2

( fjj=j 19i1Xi'lLi (Sk)g

by replacing YIk-Ak -k-Mk (Wk)

YIk-AkMk-Ak(Wk),

formula

which is

easily

calcu-

[70, 71]

Vaf (a) Yjm(et)

-Ti -1 (f(a)

I+ I

particular

we

f(a)

f (a)

+

[T

x

Yj-j-(et)]j,,.,

a

+ I

:21EI++11: In

a

spin-orbit interaction,

( aTwul,

gradient

vector

+ fvs

By using Eqs. (A.41) and (A.34)-(A.37),

-

-

aa,

I

differential operator V,, a

the matrix element for the

in

a

a

(219Bs

+ iv-s

!,, (a-v 2-

=

a

'9

aax

a,,, a-,

of

of the relation

-

1f (a)

[r

X

Y

(A.42)

a

obtain

Yjm(a)

aa A

-(21 + 1)

V I--11 (1/-t1mjI-Im+tt)Yj-jm+, ,(a).

(A.43)

Appendix

262

A.3 Correlated

Gaussian-type geminals general correlated Gaussian-type geminals calculated from the equation

The matrix element for the of

Eq. (6.26)

be

can

(W, BI k r) 10 1 f,,, (A, B, R, I

7

N

N

3

3

i=1

exp(

iP

IiZBR

t,. n ,,

p

p=1 j=1 q=1

-

qn,',

anip

ff H H H yt-i

3q

-

iR

-

2

liiBk 2

-

Pk)

(g(t+B'k;X+B',r)101g(t+BR;A+B,r)) tj=O' -=O

(A.44) It is crucial to know the

generating functions on i multiple differentiations. As

(tj,...,tN)

=

polynomial

as a

most

of the matrix element in the

dependence

of at most

can

be

degree

important operators 0

=

seen

2 in

=

from Table

exponential

J(fvr

I and

P

and

-

S).

%,...'t') 7.1, they

to do

appear

functions for the

The matrix element

for the Idnetic: energy has an additional factor which is again quadratic. The basic elements of the t and t' dependence include ti-tj, -ej--ej, ti.-ej,

and

S-ti, S-tj. As

the differentiation

the Cartesian coordinates no cross as

tip

and

can

%

,

be made

and

as

separately in each of

the basic elements have

terms in different directions of the Cartesian coordinates such

tiltj2,

x, y, and

possible

it is z

to do the needed differentiation in each of the

components.

The above considerations reduce the

operation prescribed in Eq. problem given in Exercise A.5. The for(A.44) mula developed in Exercise A.5 can be applied in each of the x, y and z components to complete the operations needed in Eq. (A.44). It is not difficult to extend the formula given in Exercise A.5 to get the matrix element for the Idnetic energy which has an additional polynomial of degree 2. In fact, Eq. (A.169) can be generalized to a relation which is valid for a general function: to the mathematical

( cNf (X1

,X2,...,

XK))

xl=o,---,XK=O

AA

Spin

matrix elements

263

N

(W#-N f (AA AA N!

f (AlZi A2Z,

27ri

A.4

Spin

AK

...

'O))'&=O i

AKZ)

(A.45)

dz.

ZN+I

IZ1=1

matrix elements

The interaction may depend not only on position coordinates but also on intrinsic degrees of freedom such as spin and flavor.. By represent-

ing the single-particle spin function by Im element is given by

(MI I o't, I m)

=

.1

V_3 (.12 m I IL 1

The matrix elements for

2

m!)

=

1/2),

a

basic matrix

(A.46)

-

spin operators, (S'AF 10,,,,, (spin) I SM),

axe

by using the Wigner-Eckaxt theorem (A-12). Here a usually reduced matrix element which is needed to evaluate the matrix element evaluated

is the

one

for Pauli matrix and it is

o-

2

given by

(A.47)

2

spin function discussed in Sect. 6.4 no technique involving angular momentum algebra is needed to obtain the spin matrix element. An elementary, direct method enables one to calculate the matrix element. We list the spin matrix element that appears in evaluating the nucleon-nucleon potential energy. For the

(Tr l M12 1 0"1 X

*

a2

I M1 M2 )

=

3(-1)M'1"_M1jMI+M27M/j+Mf2

("2 MI I MI1-?nl I "2 Tdi) ("2 M2 1 MI2 --M2

X a212m I MI M2 (MIMf 2 1 [01 1

("2 MI I Tnf1-MI

X

(1 R I_Ml "rnf2--M2 12 m).

X (Ul (M /M-I 2 I [r 1

+

2

a2)] 1M IM1 M2

Mf2

(A.48)

JM,MII+M2I-MI-M2

Tn 1) (-1 M2 1 Tnf2-M2

X

2

3

I 2

2

MI2

(A.49)

V3

E E qj=-I q2=-l

r

qj.

Appendix

264

IJ,,,,,n, (' 2

(I q,

I q2

2

ml_ 1

q2I

" 2

M) 1

+

Jmjm,('I2 M2 1 q2I .12 m) 2 1

I I m).

(A-50)

(IMIMI 1 2 i(T*0'2)(al)m+(r*0"1)(0'2)-raiMlM2)

f (-l)M2-M2 JM?M'j-MIrM2-M2

3

+

(-I)M,

1

-MI

JM7M2-M27MI-M'I'

(I2 mi I m---7n, 1

x

(al M12 I (r'0'1) (r 0*2) *

X

*1 2

Tn/1) (I2 M2 I m'--Tn2 2

MI

Tn2)

=

3

1 7n/1 -'rnl rMl-M"1 rM2-M'2 (I 2 TnI

2

7nf2)

(A-51)

(-J)MI-MI+M2-M2 2

Mf1 )(1

2

Tn2 1

TnI--Tn2j 2

I 2

MI)2

(A.52)

(al M2 3

[T X O'll I

[r X O'21112m IMI M2

X

(.12 mi 1 m--7n,

2

7nfl) ("2 M2 I Tnf2--Tn2

2

7nf2

7'ql 7q2(l qj+m'j-mj 1 q2+rn"2 -M2

X

12 m)

ql.=-l q2=-l x

(I q, I m'j-m,

ql+TWI--rni) (I q2 I m'2--M2

q2+m/2-M2) (A.53)

Here

r

is

a

3-dimensional vector and rn stands for its

spherical

com-

ponent Matrix elements for the isospin part same manner.

can

be obtained in

exactly the

A.5

with

Three-body problem

A.5

Three-body problem spin-orbit forces The matrix element for

tensor and

central,

with

spin-orbit forces

central,

265

tensor and

N-body system can be derived from the previous sections. In order to illusthat there alternative trate exist possibilities, here we use a sligthly different way of calculating the matrix elements for three-body problems with central, tensor and spin-orbit forces. In this approach the radial and angulax integrations are done separately and this involves the extensive use of angular momentum algebra. Needless to say, this approach cannot be easily pushed far. One may try to attempt to derive similar formulas for the four-body case, but to go beyond that general

formulas

in the

to be too tedious.

seems

choice

(i) a

an

presented

of basis functions

The trial function is taken in the form

TfJM,TTMT(123)

C,,,,A p ac(1, 23)

(A.54)

ac

with

expansion coefficients Q, and functions A o,,(I, 23) that are fully antisymmetric under the exchange of particles:

constructed to be

Aw,,, (1, 23)

Wc (1,

23)

oac(l, 32)

(the

construction of

+ W,,, (2, 3 1) + W,,c (3, -

(pac(2, 13)

-

12)

(pac(3, 21),

(A-55)

function is the same, but then the last three terms should have positive sign in the above

equation). function in

totally symmetric

a

The basis function a

Jacobi channel k

stands for

wave

W,,(k,pq) represents a specific (k 1, 2,3) (see Fig. 2.2). The =

wave

nota-

system where the particles p and q axe first (k, pq) connected and then the center-of-mass of the (pq) pair is connected

tion

with the nel, X (k)

particle ==

a

k. Thus the coordinate used in the kth Jacobi chan-

JXk, Ykb

is

given by MpT'p + Tnqrq

Xk

=

Tp

-

rq,

Yk

_

(A-56)

rk.

Mp +rnq Yk I in this section, instead of denote the first and second Jacobi coordinates.)

(Note

that

we use

f Xk

The basis function and isospin parts:

,

o,,,,(k,pq)

is

given by

a

(k)

Ix 1

product

I

X(k)I, 2

to

of space, spin

Appendix

266

'

FL'(kpq)

W,,r (k, pq)

where the

x

X'(k,pq)]jMj?7TtM,(k,pq), S

correlated Gaussian of the

is chosen to be

a

(-2 ;(-k)

Xk

spatial part

(A-57)

form

.FL'ML (k, pq)

=

exp

Ax(k)

2v+,\ 2n+l

Yk

YL' ML ") (iik, Vk) (A.58)

witil

'3

(

A=

62

6

0)

(A.59)

YI (Vk)ILML

(A.60)

-Y

and

L('ML Oik

-

k)

Y

The index

a

=

[YX(ik)

stands for

a

X

set of discrete labels

a

=

(Y, n, A, 1)

and

for the matrix A which contains the nonlinear paxameters 0, -y7 J. Here Y, n 0, 1, 2,..., while A is the orbital angular momentum of =

and q, and I is the orbital momentum between the center-of-mass of the (pq) pair and

the relative motion between the

angulax particle

the

particles p

k.

The index

c

denotes the labels

(L, s, S, t),

where L is the total

angular momentum, S the total spin, and s and t are the spin and the isospin of the (pq) pair, respectively. (The total isospin T

orbital

quantity, so that no T-mbdng is the trial function.) The spin and isospin parts axe thus

is here assumed to be

considered in

a

conserved

given by S

X S M, (k, pq)

=

,qTtMT(k,pq)

=

(k)] sm,

(A.61)

[?7t(pq) xqi(k)1TMT,

(A-62)

[X, (pq)

x

Xi 2

2

where Xsm (pq)

,qtm (pq)

[Xi (p)

x

X.1 (q)

2

[77.1 (p) 2

2

x

(A-63)

q.1 (q)jtm. 2

The function o,,, (k, qp) is obtained from p,,, (k, pq) by changing the sign of xk and the order of couplings in the spin and isospin functions. The sign change of xk results multiplication by the phase factor functions change as follows:

in

a

change of J to -J and spin and isospin

and the

A.5

Three-body problem with central,

XsrrL(qp)

(-1)1-'X ,,,(pq),

iltm(qp)

(-1)1-lqtm(pq). p,,,(k, qp)

Hence the function the

sign

of 6 and

267

spin-orbit forces

tensor and

(A.64)

V,,,(k,pq) by changing

is obtained from

by multiplying by

the.

phase

factor

(-I),\+'+t.

The kinetic energy operator with the center-of-mass kinetic. energy subtracted can. be written in terms of the relative coordinates as 3

2

0

0

A

-Tein

Trel

'k

k)

2rni

(k)

Yk

(A.65)

=Tk,

21j,2

where

(k) III

This

Mprn,

(Mp + Mq)Mk

(k) 2

mp + ni., +

Mp +Mq

(A-66)

Mk

is valid in any of the kth Jacobi coordinate set.

expression

basis

(ii) transformation of the

function

We, have to calculate the matrix elements between the basis functions To expressed in terms of different coordinate sets (1,23), (2,31), -

achieve this

one

has to transform the basis function from

coordinate set to another. This

can

be

one

..

Jacobi

accomplished by using

the

transformation Xk

Yk

)

T (kq)

where the matrices

(

X

(A.67)

q

Yq

connecting

the different Jacobi sets

U12

Tn2+rn3

T (21)

=

MS(7nl+M2+M3) (M2+M3)(tnl+M3)

MI

Mj+M3

M3

7n2+Tn3

T (31)

M2(Ml+M2+M3)

M1

(1712+M3)(M1+M2)

Tn1+M2

M3 __

tn I

I

+rn:3

T (32)

mj(mj+Yn2+Tn.3) (tnj+mj)(Tnj+tn2)

M2 "Ll

+TrL2

are

given by

268

Appendix MI -

M3+Mj

T(12)

TrIS(Ml+M2+M3) (7n3+7nI)(M2+7n3)

7

M2

M2+M3

MI

MI+M2

T(13) 1112(IILI +IIL2'1-11L.1)

?IL'j

(7rII+M2)(?tL2+7J'L.3)

"12 +7,11.3

_M2

MI+M2

T (23)

(A.68) MI(MI+M2+M3) (Tnl+Tn2)(M3+Ml)

M.4

M3+?nI

The space function TLc'M,, (k, pq), expressed in the kth Jacobi coordinate set, can be transformed to the one expressed in terms of the

qth Jacobi

coordinate set

as

follows:

TL'M (k, pq)=1: L3(kq) (ad),TLagr (q, kp), L 11

(A.69)

,

ry

where

,

MI,

(q, kp)

=

exp

(_2

)

and where a stands for 2P +

+ 2h +

The matrix A is

(A.67)

F

=

a

set

X

2V+X q

Yq2fz+Ty(Al) LM ,

2v + A + 2n + 1.

uniquely

(A.70)

(T/, ii, , 1), which has to satisfy the relation

(A.71)

determined from A

by

the

transformation

as

j_(kq) AT(kq) The the

Q, (X q, Yq

6(kq) (ad) L

in

(A.72) Eq. (A.69)

is the transformation coefficient of

polynomial part: 2v+.k X

k

Yk2n+Iy(AI) LML, (Xki Yk

EB(kq)(ad)X2F/+XY2Ft+Ty(XO (XV Yq -

=

L

q

LML,

(A.73)

a

To get this expression one has to make. use of Eq. (6.7) and to recouple, the product of the two angular functions (see Complement 6.3) by

A.5

with

Three-body problem

[y(1112) (:j,

)

12

X

central,

tensor and

spin-orbit

forces

269

y(1314-) (:j, )JLM 134

Ef 1121121314-134L y(113124) (:j LM

(A.74)

113124

113124

where the coefficient E is ficient C of

Eq. (6.11)

given by

a

unitary 9j symbol and the coef-

as

11 13 113

El'- 121121314134L 113124

12 14 124

112 134

Q11 13; 113) C(12 14; 124) (A-75) -

L

Note that the coefficient E may be defined

by the reduced

matrix

element -

-

121121314134L N 2L T 1 Ell 113124

(k '/2L + I (y(113124) LM

y(1112) (60, ) I 712

C

X

y(131A) I

)JLM)

,34

=

C ' ) 11 y(1314)( (-j)112+134-L(y(113124)(XA' ) Y(1112)(:j 134 112

=

(-1)13+lA (y(1112) (:j, 1

L

y(1314) ( C'

y(113124) L

12

34-

(A.76) which is

(YI

easily verified by using Eq. (A.147)

" 1) v/2k + I QW; k)

Y1,

Yk

and the relation

V21 + I C(kl'; 1). The transformation coefficient

(kq) BL (aa)

B(kq) (Cla) L

(A-77)

is then

expressed

as

nI &I- X2,XI1121L D"X D V1XIV2-X2 nj1jn212

X[

vl"*-1"2-"2 njIjn2I2

X

X

T(kq))21/1-+Ai(,p(kq) -

22

where the coefficient D is is constrained

)

kq) 12

21/2+1\2

(T(kq))

2n1+11

21

2n2+12

(A.78)

I

given in Eq. (6.8) and where the summation

by the conditions

2vl_ + A, + 21/2 + A2

=

27/ +

A,

2n, + 11 + 2n2 +12

=

2n +

11

Appendix

270

2vi + A, + 2n, + 11

=

X,

2 i+

2v2 + A2 + 2n2 +12

=

2Tz +

17

(A.79) and

the

triangular inequality for the angular momentum among (/XI7'X2iA)7 (11712 07 (Al 117 X) and (A2 12 1), respectively. The transformation to the pth Jacobi coordinate set can be per-

by

7

formed

well in

as

a

similar

The spin part of the

1

.

7

manner.

wave

function transforms

as

(-l)'21+'-SU(.! ISI; gs)X SIVIS (q, k-P)

X8S Ms (k, pq)

22

E(-I)'!+-SU(.!

-IS-!; 2 sft S Ms (p, qk).

2

The transformation of the

2

22

isospin part

is

given

in

(A.80)

exactly the

same

way-

The radial and

However,

no

such

appears in the

integration

angular integrations are separated in this approach. separation is made hi the factor e-6xk-yk which

exponent of the has to

one

function.FLIM,: (k, pq).

expand this

term into

Therefore in the

partial

waves

(see Eq.

(6.53)): ,-wx-Y

where

ii(x)

(6.48)

and

radial paxt

=

v"2-1-+I e(l, w) il (I w I xy) 01) 100 (--

4r

(A.81)

7

is the modified

E(I, w) one

=

I for

encounters

spherical Bessel. function of the first kind w rel="nofollow"> 0, 6(1, w) (-I)' for w < 0. In the of the form an integral =

cc

fo

I(n, 1, v, I w

2n+1+2

Y

Ivy 2

e-2

r-(2n)!! w I' -2 vn+l+a2 where

n

guerre

polynomial (10.15).

is

a

eXp

ij(jwjy)dy

(W2 ) L('+'!) ( W2) 2

n

2v

non-negative integer and

2v

Ln(')(x)

We define the

(A.82)

is the associated La-

following integral

I(v, n, 1, u, v, IwI; V) 0

fo JO

CO

X

2v+1+2

2n+1+2

Y

1

e-

UX2

_

IvY2

V(x)il(lwlxy)dxdy

Three-body problein

A.5

with

central,

tensor and

spin-orbit

forces

271

00

1

x

2u+1+2

IUx2 F

--

e

(A.83)

V(x)l(n, 1, v, lwlx)dx.

0

The one-dimensional

integration

the functional form of

ated. In the

special

V(x),

case

can

when

be

V(x)

I(v, n, 1, u, v, IwI; V=1) n

X

equation, depending on analytically or numerically evalu-

in the above

=

1

we

obtain

(2n)!!F (n + I +

8

V

F(k + U + + 1) 2 kl.(n k)!F(k + I +

2v

w2)

2 2

where F is the Gamma function

given

in

we axe

(k I q)

,

(A.84)

Eq. (7.8).

ready

to calculate the matrix elements. The

tween the functions in different Jacobi sets k and q

separately

k+v+l+A2

matrix elements

(iii)overlap Now

n+l+ 2

(w2)k

-

k=O

3

2

in the space,

=

spin and

can

overlap be-

be calculated

isospin parts:

( pc(k, pq) I Wycl (q, kp)) "I" 0

=

X

JLLI JSSI (.FL'ML (k, pq) I )7LMI (q, kp))

(X'SMS (k,pq)IX" SMS (q,kp))(,qtTm,(k,pq)lqt

m,(q,kp))(A.85)

The

spin part

is

easily obtained by using Eq. (A.80)

(X'SMS (k, pq) I X" SMS (q, kp))

=

(- 1)

" +'-S 2

as

.1 S U (.1 .1; 2 22

s's) -(A.86)

Likewise, the isospin part becomes

(,qtTM, (k, pq) lqt'TMT (q, kp)) The

ing

integration

=

( _j)-!+t-TU(I22ITI; 2 tt). 2

of the space part

the function in the bra to the

performed by transformdepending on the qth Jacobi

can

one

be

By substituting Eqs. (A.69) and (A-70) we obtain (the label the coordinate set is suppressed in the integral)

coordinate.

suffix q to

(A.87)

(-'FL'ML (k, pq) I

"

(q, kp))

=

E L3(kq) (aa) L

272

Appendix

X

if

x

2P+X+2Y'+)L" 2fz+[+2n'+I'- 2IUX2_lVy2_WX.,y e

y

(Y'X) oi, m) *Y(""/

X

LML

dx dy

LML

(A.88)

with

U= +o

=!+-t

V

The

angular integration

and

(A.74)

(YL(

easily by

(A-89) the

use

of

Eqs. (A.81)

can

ML

( C' m

d

L ML

_X-+ +I1,E(r w) Ety.OX'1"LL i.(Iwlxy). V2_x

4w

One

be done

=S+j'.

as

e- wX-Y

and then

can

w

(A.90)

easily verify that 1+1'-r, has to be even and non-negative, the integral formula (A.84) to obtain

one can use

(.FL'ML (k, pq) I

"' -1

LML

(q, kp))

4y"13(kq) Ir

,

X

I

X + 16 (M' W) EX"jj'-0,X'1 K Vf2-1

L

(P+vl+

"

LL

A+AI-K 2

2

'K,U, V,

IWI;

V=I) (A.91)

(iv) matrix elements of kinetic energy operator The next step is the calculation of the matrix elements of the kinetic energy operator

(k ITrel I q)

=

(W,, , (k, pq) ITq I W& d (q, kp)).

In the above

erator

can

(A.65)),

expression be expressed

and thus

we

(A.92)

used the fact that the kinetic energy opin different relative coordinate sets (see Eq.

we

defined Tr,,l in

conformity

with the coordinate

set in the ket. To calculate the matrix elements of the kinetic energy

operator

one

(X

first notes that

2v+.X

2n+l

Y

e-.21 ,6.2_:I_YY2_,E._y YLM

A.5

with

Three-body problem

30X2 X X

-2(

x

central,

02X4 + j2X2Y2

+

21/+)L-2

2n+1

Y

e

x

20(2v + A)X2 LM

e

1))

4 M 7F

13X2)

I

LM

+

+I

(2v

-

Ox 2)

x

proof of this

2Y(2z/ + 2/X +

EU(A-I1Ll;AK)C(11;K)Y('X-I

-V2A A

+

273

F3

1, _.L,3X2_ YY2_,5x.y 2

(2v + 2A +

X

-

spin-orbit forces

2_1 --Ox ilyy 2_,SX.y Y. (,Xj) 2

2v+X-1 2n+l+l

Y

tensor and

(A.93)

LM

relation is

given

in Exercise A.6. A similar

expression

holds for the second relative coordinate y. By the help of the above equation the effect of the kinetic energy operator applied on the basis function is

given by

a

linear combination of terms akin to the basis

function. The matrix element of the kinetic energy can therefore be given by repeatedly using the expression obtained for the overlap of the basis function.

(v) matTix

elements

The central V

=

=

of central potentials two-body interaction can be

V(I'r2

V(Xl-)

that is, the

7'3

-

+

1)

V(Irl

+

V(X2)

potential

is

+

-

T3

1)

+

V(jrI

as

-r2

1)

V(X3)

a sum

of terms

coordinate in different Jacobi sets. In for the

written

(A.94) depending on the first relative calculating the matrix element

case

(k I V(xp) I q)

=

( O,, (k, pq) I V(xp) I Wa,,, (q, kp)) -

JLLIJSSI(-'r-7LaML (k, pq) I V(xp) I.F&L (q, kp)) X

(X'SMS (k,pq)IX" SMS (q,kp))(TItTm,(k,pq)lqt

m,(q,kp)),

Appendix

274

(A.95) the

spin and isospin paxts

can

be calculated

as

before but the

spatial pth

functions in the bra and the ket have to be transformed into the

Jacobi coordinate set in which the potential is defined. The space paxt of the matrix element is calculated transformations k -+ p and q --+ p:

by using

the

"'

(FL'M,,(k,pq)IV(xp)l J,w, (q,kp)) L3(qp) (ala/) L

B(kp) (aa) L

(-'FL'M.,,(p,qk)IV(xp)IFL'

x

Here the matrices

corresponding

(A.96)

(p, qk)).

to the transformations

axe

defined

by T(kp) AT(kp)

A'

T(qP) A!T(qP)

=

(A.97)

respectively. By introducing +

U

one

+7

V

j+

W

(A.98)

&I

obtains

(.FL5'ML (p, q k) I V (xp) 1.FL 4 jr

X

IL

(p, q k))

/-2-r.+1,E(n, w) Et nOXI'P'LL

I(P+Vf+

+

ii+?P+ 2

2

K) U, V,

IWI;

V)

-

(A.99) (vi) matrix

elements

of tensor potentials through

The tensor interaction is defined

SP

2 /-4r

V -5 (Y2 (ip ) [O'q '

X

Crk] 2)

-

the tensor operator

(11.7) (A.100)

A.5

Three-body problem

with

central,

tensor and

275

spin-orbit forces

To calculate the matrix element of the tensor interaction

one

has to

same steps as for the central interaction, except that now part of the wave function has to be taken into account, and the

follow the the

spin spin part should as

the

one

potential.

also be transformed into the

The

use

of the

coordinate system theorem (A. 14) enables

same

Wigner-Eckart

to obtain

(kjV(xp)Spjq)

-=

(W,,(k,pq) IV(xp)Spl W,,,e(q, kp))

U(L2JS; LS) ',E47 VF(-2L+ 1) (2S' 1) 247r 7r r 5

+

x

II (,)7L' (k, pq) II V(xp) Y2 (x-) P

x

(X'S (k, pq) II [Cq

x

(nTtMT(k, pq) Iq tm, (q, kp)).

X

FL',f (q, kp))

O'kj 2 11 X'S/ (q, kp))

(A.101)

spatial part of the matrix element is calculated as before by transforming the basis functions to the pth Jacobi coordinate set Here the

(Jc'L'(k,pq) 11 V(xp)Y2( p-) Ij.FL,(q,kp))

13() (a& ) L'

13(kp) (ad) L

x

II FL',f (p, qk)), (YL' (p, qk) I I V(xp) Y2 (x-) P

where the last term is obtained

(JC L"(p, qk)

V( Xp) Y2 (Xp) ip

4ir

X

by using Eqs. (A.81) i

(A.102) and

(A.82)

as

(p, qk))

V2- r, + 1 c (r., w)

(YL' 1)

YO

0

Y2 (-

O)

YL

ii+?P+

X

2

2

r" U, V,

IWI;

V) (A.103)

Here u, v, w are defined in even and non-negative.

Eq. (A.98).

Note that

f+

r,

has to be

276

Appendix The reduced matrix element of the

using

6.3)

angular paxt is calculated by recoupling technique (see Complement

the

and

angular momentum Eq. (A.76). One obtains

YO (I

( Y.,L

K

YL(XI F) ( c

Y2 ( 0)

I

U(2n2r,; WO) Q2K; W) Kf

X

(YL

Y2

01

Ll

/2r,'+ 1

EV

2K+I

C(2r.; K)EX LXII,-'L2.

(A.104)

The

spin matrix element is also easily calculated by transforming the spin functions to the pth Jacobi system and by using Eqs. (A.147)

(A. 149)

and

as

(X'S (k, pq) 11 [Crq =

X

Uk]2 11 X" S" (q, kp))

E(-l).2k+g-SU(-nS-1; S) E(-1)-!+""-S'U(.! 2

22

X

(X S (p, qk)

[G'q

X

2

Ok] 2 11

22

XS P, (p, qk)),

2

(A.105)

where

(X S (p, qk) 11 [Uq

X

Uk12 11

XS P, (p, qk))

(2S + 1

(_I)s,,-St+s-g V X

(("221) 9 11 [O'q

X

29+1

U(Ii S2; S'9) 2

UkI 2 11 ("22'0 i

(A.106)

with

(('1'1)9 11 [O'q 22

X

4+ (vii) matrix The

Uk12 11 1

elements

spin-orbit force

22

2

2

1

1

1

1

2

2

8

2

(,V6) 2 =2v/_5JgjJ pj.

9

of spin-orbit potentials given through the operator (11.9)

is

(A.107)

277

A.5 Three-body problem with central, tensor and spin-orbit forces I

with

LV Sp -

As in the

Lp

=

-ixp

Sp

Vp,

=

2

(0'q+ffk)- (A.108)

of the tensor interaction, with the

case

Eckart theorem

(A.14)

(kjV(xp)Lp-Spjq)

one

_=

use

of the

Wigner-

obtains

( o,,,(k,pq) IV(xp)Lp-Spl W,,,,(q, kp))

U(L'lJS; LS)

r

+ 1) + -1)(2S' V-(2L x

x

(FE'(k,pq) 11 V(xp)Lp 11 FL, (q, kp))

(X'S (k, pq) I I Sp I I X'S, (q, kp)) (,qtTMT (k, pq) lqt'TMT (q, kp)).

(A.109) spatial part of the matrix element is calculated as before by transforming the basis functions to the pth Jacobi coordinate set

The

V (xp) Lp

(.FL' (k, p q)

L3(qp) (af&i) LI

L3L(kp) (aa) x

YL, (q, kp))

(.FL5 (p, qk) 11 V(xp)Lp 11 Jc'L",(p, qk)).

When the orbital

angular

momentum

(A.110)

operator

acts

on

the basis

(provided both the basis function and the operator in the same coordinate system) one obtains

function

pressed L

(x

21/+X 2n+1

Y

ij(x

X

A0 e--21- '3X2 _!IY _IYI _,5X_y YL(M

Y)X" +A Y2n+l e_21,3x

2v+,\ 2n+1

+X

Y

Note that the outer

vf2-[x

x

yll_,,

=

axe ex-

1)3X2

1 _

e- 2

'f

YY2

product i(x

X

(4-\,F2-x13)xyYj(,',1)

2_1

'YY

2_dX.y

YLI'Xj) (ic M

A0 -6"YLYL(M

y),, ).

is

equal

(A.111) to the tensor

Therefore the

product

spatial part

of

tained in

element, (.FL6(p, qk) 11 V(xp)L, 11 J:L` ,(p, qk)), can be obexactly the same way as in the central potential. It is given

by

of two terms: One is

the matrix

a sum

4vf2-7 J

47r 3

X

vf2-_K+I c (K, w)

(YL` r) ( C' m I I YO(Kn) ( C' m YI(I-I-) ( C' m I I YL(" F") (:t' o

278

Appendix

(P+1/1+

X1

n+W+ 2

K) U, V,

2

IWI;

V)

(A.112) and the other is

v/2 r. + 1 E (r,, w) (YL(

4-,T

YO(MM) (i

,

Fj+P+

X

fi+??+ 2

L

KI U1 V,

2

II

YL(fk'[')

IWI; V (A.113)

Here u, v,

defined in

Eq. (A.98). Note that in the first term and non-negative, and likewise in the second term I + 11 r. has to be even and non-negative. The angulax part in the first term can be obtained by using Eqs.

T+ P

+ 1

w

-

axe

r,

has to be

even

-

(A.74)

(A.76)

and

as

YO( MIS)

(YL

YI(l 1)

YL

(A.114)

pq

pq

The

angular part

(YL(

( b,

in the second term becomes

YO(K n)

YL(',"

L

i, L

L

YL(, "")

(A.115)

where

(YL(X"")

L

(_,)L-L" V

YLI 2-L+ 1

U

2XI +I

L 1; L'XI) (I

Xi,

i

L

YX, ( b)

(A.116) with

(Yl(;k) 11

L

11 Yl(.-b))

=

0(1 + 1)(21 + 1).

The spin matrix element action. The result is

can

be calculated

(A.117) as

in the tensor inter-

A.5

Three-body problem with central,

(x'S (k, pq) I I Sp I I

tensor and

spin-orbit

X'S'/ (q, kp))

-21+-SU('.!S.1; Sg) E(-I) 12+S'-S'U(.1 22

1

22

2

x

279

forces

(X S (p, qk) 11 Sv 11 X S-', (p, qk)),

S' 1;

(A.118)

where

(X'S (p, qk) I I Sp II X'S'f (p, qk)) S+I

S+IU (Iksi; Sg) =29+

-S,+S-

X

2

1

2

(A.119)

(("I22'1) 9O'q + Uk I I (I22'I) k)

with + O'k ((*"1) 22 9O'q

22

R)

8+1 E: 122 U(-! -191; '9

2+

206-JgJi j.

06-1) 2

((- 1)

-j;

+

1) (A.120)

280

Complements

Complements A. I Mabix elements

central

o

potentials

The matrix element of the central and tensor

potentials

can

be ob-

tained

through a step which is slightly different from the procedure presented in Appendix A. 1.3. Then the formula becomes simpler than Eq. (A.21). Here we outline the step which leads to this simpler result. Instead of using Eq. (A.19), we first perform the integration over the angle i6 in Eq. (A. 17), which leads to Tj I r2

(fK'LIMI (7Z, X, X) [

r)

YxIL ( ri

-

rj ) I fKLM (u,

A, x))

3

47r

(2r)N-2

BKLBKILI

detB

_.LCT2 e

X

x

[

A2

+

q/A/2 +

c) if

d& d

'

d2K+L+2K+L"

YLMWYLIMfO )*

exp

2

dA2K+LdA/2K'+Ll

AA/e. et] in (rV)Y"'j#Y)

(A.121)

Wi0 V

=

-tAe + -Y'Ye'.

(A.122)

If either -y or -y' vanishes, v is independent of the scalar product e-e', and the integration and the differentiation prescribed in Eq. (A.121) becomes very easy. When neither -y nor 2 exponent can be expressed in terms of v

qA2 + qiA/2 + pAA'e P

2 V

+

2-y-y' One first has to

-

-y'

is zero, the term in the

as

e'

(q_ 2-y

expand

A2

+

(qf

A 2) i,,,(rv) exp(2-y,,1V

A/2. 2-/

in terms of powers of

(see Eq. (6.48) for the expansion). Secondly, multiplied by the spherical haxmonic the

coupled

(A.123)

its

general term v expanded

must be

v

2n+n

in

The second step can [YL ( -_) x YL, (,E )] In this derivation one can avoid Eq. (6.7).

tensor form of

be done with the

use

of

recoupling the angular momenta, and hence would get the simplest possible formula for the matrix element.

CA. 1 Matrix elements of central potentials In the

with

x

make

following we work out the details for the central potential However, we shall not follow the above route exactly but

0.

=

a

281

little detour in order to make transparent the relation to the To this end we rewrite the left-hand side of

overlap matrix element. Eq. (A.123) as follows:

A2 + I A/2

+

pAA/ e. e/

qX2 + q'A12 + PAA/ e. e

=

2c

V2. (A.124)

V2

The term Hermite

2c

e

jo (VV) is expanded in

powers of

v

with the

use

of the

polynomials: V

V

2c)

exp

-

i o (r v)

=_

2c)

exp

1

-

2rv

(e'r

V

-rv)

e

-

00

V22 r) (V2c2)n. C

,,F2c Next

we

expand

exp q A2 +

q' A/2

n=0

exp

+

(2n + 1)!

H2n+l

c,

(qA2 + q'A/2 + pAAI e. ef)

p,\A'e

H(p -ra, qA2)H(pI

e'

-

-

) (2c V2)n -

2c

as

follows:

ni _

(2

n , q'A/2 )H(I

H(M' 2A2 )H(a, 7/2,X/2 )H(n

(,,2,)n

(A.125)

m

PPIIMMI

-

-

n

+

+

m

m', pAA'e-e)

a, 27-yAYe-e)

1: FPnPj (c, q, q, P, t,,Yf),X2p+'A/2p'+l (e-e')'

(A.126)

PPfj

with n!

Fpnp,,(c, q, q, p, 7,7')

1: H(p

=

-

m,

q)H(p

I -

M

Iq

MW

7

x

Here p, p, I,m, and m' are all of their values are determined m <

is

p, ne <

now

n+m-nz!

H(I -n+m+m',p) 2m+m'm!

(fK' L' MI (Uf, X) X) I V(I Vi

(n

-

m

-

ne)!'

(A.127)

non-negative integers and the

ranges

the conditions p + p' + I > n and + m! < n. The operation in Eq. (A. 121)

p', n I < m easily done, leading to -

ml 1.

in-m+m'

7

by

the result

-

'rj 1) 1 fKLM (U, A, X))

282

Complements

(2K + L)! (2K'

JLLIJMM'

+

L)!

BKLBK-'L

K+K+L

2

(2

E

detB

J(n, c)

n=O

min(K,K")

E

X

Fk7-k KI-k L+2k (c, q, q

A'Yi

^//) BkL

(A.128)

i

k=O

where

J(n, c)

is the

integral defined by I

J(n, c)

= -

-V/7-r-(2n + 1)! "0

f V(jx)e-X2HI (X)H2n+l(X)dX-

x

In the

overlap

case

of

V(r)

=

matrix element

comes nonzero

(A.129)

C

0

if and

I the formula

(A.6),

only if n

(A. 128)

reduces to that of the

because then the

=

0 and

integral J(n, c)

be-

FF2k Kf -k L+2k (c, q, q, p, -Y, -y')

k, q)H(K' k, q')H(L + 2k, p). Though this relationship is not apparent in Eq. (A.21), both equations should give the same result for the central potential. For the special case with K K' 0, Eq. (A.128) reduces to a much simpler form which essentially includes a double sum: reduces to

H(K

-

-

=

(fOLM (U =

I

=

A! 7 X) I V(ITi -rj 1) 1 fOLM (u, A, x)

(fOLM(W,X,X)jfOLM(u,A,x)) L

X

1

D

77

n

E (L-n)! ( cp )

J(n, c),

(A.130)

n=O

where the

overlap (fOLM(UIiWiX)jfOLM(u,Ax)) is given by Eq. a particularly nice feature for power (A.7). k law potentials V(r) because then the c-dependence of J(n, c), r The above formula has =

,

now

denoted Jk (n,

c),

is factored out

as

follows:

k

Jk (n C)

=

(2)

2

Vir(2n + 1)!

C

(2) C

00

-2

k 2

n

1

7,=, E

M=0

fo

X

k+I

ai2n+l

( dX2n+1

2% -X

-e

(-l)m22n-2m+l mI(2n-2m+I)!

-V

n-m

+

dx

k+3). 2

(A.131)

CA.2 Matrix elements of

283

density multipoles

j are contained only in c and -y-y'lcp, this factorization makes the summing up of Eq. (A.130) over i and j much faster. Especially for the Coulomb force (k -1), we get Since the

indices i and

particle

=

2c

J-1- (n, c)

(-l)n (2n + 1) n!

(A-132)

-

-x

potentials the route given below Eq. (A.123) leads following simpler result including only a single sum:

For other types of us

to the

(f0LM(UIiWiX)jV(jri

-

rjj)jf0LM(UiA7X))

(2L + 1)!!

(27r)N-1

4v

detB

L

)3 1: 2

n=O

I

L!

n!(L

77

-

n)!

n L-n

c

00

2n+2 X

V'r(2n + 1)!!

10 V(eX) X2n+2

e-'2dx.

(A.133)

C

particular simplicity occurs for a Gaussian potential as e-'2, we obtain perform the n sum easily. For V(r) A

one can

then

=

(ALM (U X X) I eXP I_ X(r, i

i

_,rj)21 IfOLM(U7 Ai X)) 3

(2L + 1)!!

(21r)N-1,

4v

detB

3

f

-I

)2

+

2r,) (P C

L

7,y + C

i+

(A.134) of density multipoles Here we Eq. (A.30) takes a simple form for the special case K' 0. As we have seen in the chapters of applications, the of K 0 is, with the use of its fall general A correlated Gaussian with K matrix and u vector, a very useful basis function. The simplified form A.2 MatTix elements show that

=

=

=

of the matrix elements

was

in fact used in

our

calculations. TrI the

and

case

in order to have

even 0, L nj n2 has to be non-negative the term from contribution -n2) /2, q). H((2K+L-ni non-vanishing the other On and even. Likewise Lf n3 has to be non-negative nj of Eq. (A.20) becomes nonhand, the recoupling coefficient Rnin2n3 LLIr.

of K

=

-

-

a

-

-

L' and n2 + n3 K vanishing provided that ni + n2 L, n, + n3 are all non-negative and even. Therefore we are led to. the result that L the summation in Eq. (A.30) is restricted to the case of nj + n2 L n and L. By renaming nj as n, we obtain n2 and nj + n3 -

-

-

=

=

=

-

284

n3

Complements

=

L'

n, where

-

from 0 to

n runs

min(L, L').

limited

by the condition that n2 + n3 non-negative and even and also K > max(IL are

the

-

triangular relation

n

=

-

Possible values of L + L'

LJ, IM

2n

-

-

of the Clebsch-Gordan coefficient

-

is

is

be

M'j) (L M K AV-

due to

MIL'IW). Furthermore, L-n L-n RLL'r. n

n2

=

L

11 :!

-

12

note that under these conditions

we

is contributed

13

n,

n3

=

by

=

single

a

L'

-

n

in

term with

11

=

RnLjn2n3 L-lis

ni

Eq. (A.20). This

=

n,

12

=

=

is because

13 :5 n3 and 11 + 12 > L, 11 + 13 ! L. Using the ni, well-known formulas for the Clebsch-Gordan coefficients (10 P 0 1 L 0) < n2,

and the Racah coefficient L-n L r,; L'

U(n

[751

L-n)

(2L 2n+ 1)! (2L' 2n)! (L +L' is) 1 (L +L' + n + 1) 1 (2L + 1)! (2L')! (L + L' 2n is) 1 (L +L' 2n + r, + 1)! -

-

-

-

-

-

(A-135) we

obtain the

following

result:

(fOLIMI'(Ul X, X)IJ(17VX -r)jfOLM(U, A, X) (2T) M-2

(

=

min(L,Ll)

2

3

2

1

E pnL-nI/ IL-nrL+L'-2n

cl e-'Ycr

detB

n=O

L+L'-2n

1:

x

ZLL'nn (L M r, M

-MJL'M)

r.=max(jL-L'J, IM-M,'I) x

where

r.

Y. M'

--M

('0 *'

(A-136)

+ L + L' has to be

ZLLfnr.

-

(-1)

2

even

(L-L'+x)

and the coefficient

F 2L

ZLL'nr.

is

given by

(2 +1) 47r

T L, + L' + -+I)! JL-K)!(L K

-

x

(2n)!! (L + V

F L-(LL --+L"5; L

x

-

2n

-

n)!! (L + L'

-1i ((L ---LL++-'KS

-

2n +

x

+

1)!! (A-137)

CA.3 Overlap matrix elements for

With one can

an

three-particle system

a

appropriate choice of the (N

-

I)-dimensional

285

vector

w

calculate various matrix elements. To calculate the matrix

J(ri

element of

-

xN

-

r),

one

only needs

to set

w

equal

to

w(') which

Eq. (2.12). The values of c, p, -y, -/' are obtained from Eq. w(ij) with being replaced by 0). In exactly the same manner,

is defined in

(A.18)

one can

also calculate the matrix element of J(ri -rj -r)

the vector

w('j),

defined in

Eq. (2.13),

for

w.

By using

by employing

the well-known

formula

J(iv-x -,r)

J(Ifvxl

-

r)

Y"11

r2 r.

WX

(A.138)

Y"tt

it

Eq. (A.136) immediately enables one to obtain the matrix element of the density multipole operator J(ji7vxj r)Y,,,,(w` _x). The matrix element for the central potential, V(j ri -rj 1), is obtainable from Eq. (A. 136) as well. By integrating the equation multiplied 0 contributes to by V(r) over r, we see that only the term with n the matrix element of the central potential. It is easy to see that the integration leads us to the same result as Eq. (A.133). -

=

Overlap matrix elements of the correlated Gaussians for a threeparticle system We tabulate in Table A.1 results of the calculation for the quantity A.3

/2N-2

61, i9aili (9-rili-mi

exp

( -2IS-Bs)

(A.139)

three-particle system (N 3) assun-Ang li < 2. The vector si is defined by aj(1 2), -2-ri). The calculation was done with i 2, i(l + Mathematica [1841. The quantity apparently has a symmetry property with respect to the interchange of li, mi +-+ 1j, mj. E.g., if one calculates this quantity for a given set of angular momenta, then the quantity corresponding to a set (111 MI 13 M3 12 M2 14 M4) can easily be obtained from it by simply interchanging the suffices 2 and 3 of the B matrix. Note that the table can be used for the four-paxticle system as well if one of the angular momenta is restricted to zero. for the

=

1

,

,

1

1

1

286

Complements

Table A.I. Tabulation of vector si is defined

Eq. (A.139) for

the

three-particle system. The

*Tj 2, i(l +7,i 2), -2-ri).

The matrix B is a 4x4 by ai (1 symmetric matrix and its elements are denoted a B12, b B137 C B34. The tenth to twelfth colunu3.s give the B23, eB241 f B14, d types and the coefficients of terms needed to construct the solution, where each coefficient must be multiplied by a factor given in the ninth column of the corresponding entry. For example, in the case of 11 12 MI M2 -2, 14 2, 13 2, M3 2, M4 -2, the quantity of Eq. (A. 139) is given by 12288 x (3b 2e2 + 3c2d2 + 12bcde). -

=

=

=

=

=

=

=

11

MI

12

M2

=

=

=

13

M3

=

=

=

=

14

M4

-4

f

--

0

0

0

0

1

1

1

-1

0

0

0

0

1

0

1

0 192

f2

0

0

0

0

2

2

2

-2

1

0

0

0

0

2

1

2

-1

-1

0

0

0

0

2

0

2

0

1

32

ef

0

0

1

1

1

1

2

-2

6

0

0

1

1

1

0

2

-1

-3

0

0

1

1

1

-1

2

0

1

0

0

1

0

1

0

2

0

2

0

0

1

0

1

-1

2

1

-1

0

0

1

-1

1

-1

2

2

1

16

I

1

1

0

1

0

1

-1

1

0

1

0

1

0

1

0

af

be

cd

1

1

1

(Continued

on

the next

page.)

CA.3

(Continued

Overlap

matrix elements for

a

three-particle system,

-

from Table A. I.)

1536

def

0

0

2

2

2

0

2

-2

-2

0

0

2

2

2

-1

2

-1

3

0

0

2

1

2

1

2

-2

2

0

0

2

1

2

0

2

-1

-1

0

0

2

0

2

0

2

0

2

256

af2

bef

cdf

I

1

1

2

0

2

-2

-6

-6

1

1

1

2

-1

2

-1

9

9

1

1

0

2

1

2

-2

1

1

1

0

2

0

2

-1

6

1

1

1

-1

2

2

2

-2

-3

1

1

1

-1

2

1

2

-1

3

1

1

1

-1

2

0

2

0

-3

2

2

-2

3

3

-6 -6 3

-1

-1

1

0

1

0

2

1

0

1

0

2

1

2

-1

-3

-3

-3

1

0

1

0

2

0

2

0

3

4

4

1

0

1

-1

2

2

2

-1

1

0

1

-1

2

1

2

0

1

-2

-1

1

-1

2

2

2

0

-1

-1

-1

1

-1

2

1

2

1

1

1

b2e2 acdf

C2d2

3

3

3

12288

a2f2 abef

bede

2

2

2

2

2

-2

2

-2

2

2

2

1

2

-1

2

-2

-3

2

2

2

0

2

0

2

-2

3

2

2

2

0

2

-1

2

-1

2

1

2

1

2

0

2

-2

2

1

2

1

2

-1

2

-1

12

-6 2

2

2

-3

-3

6

-2

4

3

3

3

3

6

4

-5

-5

3

3

3

6

6

6

-2

2

2

1

0

2

2

0

0

2

2

0

0

2

2

-3

-1

0

287

Exercises

288

Exercises

Eq. (A.14).

A.I. Derive

Noting the definition of the scalar product (11.2), expanding the angular momentum coupled ket functions, e.g., Solution.

(LS) JM)

E

=

in

Eqs. (11.1) and

states of bra and

(Lm, SM2 I JM) Lrni) I SM2)

(A.140)

TaIM2

and

using the Wigner-Eckart theorem (A. 12),

((L'S') JM 1

we

have

(0,, (space) 0,,, (spin)) (LS) JM) -

1) 1'(Lm, SM2 I JM) (LW1 SW2 I JM) AMIM2M'MI 1 2

X

-vF2-L'+1 X

The

use

(L' 11 0,,(space)

(SM2K --PISIMf2) (S' 11 0,,(spin) V12--S'+1

of

a

L)

(A.141)

S).

symmetry property of Clebsch-Gordan coefficients +

(SM21S --AISIMI) 2 enables

one

(-1)IS

V

2S+1

(KILSIMf2 I SM2)

to rewrite the above matrix element

((L'S') JIVI 1 (-W

X

=

(A.142)

as

(0,, (space) Q, (spin)) I (LS) JM) -

(V 11 0,,(space) 11 L)(S' 11 0,,(spin) 11 S) + + 1) -1)(2S V/(-2L'

E

(Lm1r,/LJL'm'I)(L'm'IS'm'2JJM)

JL'ra1M2?-afIM2r x

(Lm1SM2JJM)(K.ASITnI2JSTn2)-

(A.143)

sum over A, Tn1 , M2 , MfJ , TnI2 of the product of the four ClebschGordan coefficients is just the recoupling coefficient U(Lr.JS';L"S)

The

(see Eq. (6.67)).

This

complets

the derivation.

Exercises

289

A generalization to the matrix element of a coupled tensor operator be made similarly. Let us calculate the matrix element

can

((L',5 )XM'j [01(space)

x

Ox(spin)j,,, J(LS)JM

(LIMI1 SIM/2 I JM) (Lm, SM2 I JM) (1mAp I rw) MIMMIM2MA 2 1

(Lmj1mjL'm ,f2--L'+

(L'

01(space) 11 L)

(SMALI S/ M2I) (S' V -2-Sl+1

OX(spin) 11 S).

11

The

sum over

?n j, m'2

Tn1 , M2 i M7 A

,

of the

(A-144)

product of the five Clebsch-

Gordan coefficients

(LmISM2 I JM) (1mXMjnv) (LmIlmILal) MIM2MtlMflM'2 X

can

be taken

by

(STn2l\l-tlS'M2)(VM'IS'M'21XM')

means

(JMr,vIYM')

of the

unitary 9j symbol

L

S

J

I

A

K

L'

S'

X

(A.145)

as

(A-146) _

_

multiply Eq. (A.145) by (JMr'VjYAF) and sum over M and v with M' being fixed, then what one has is a sum of the product of six Clebsch-Gordan coefficients involving nine angular momenta, and it is nothing but the 9j symbol in unitary form given in Eq. (A.146) (see Eq. (6.78)). Then with the help of the orthogonality relation of the Clebsch-Gordan coefficients Eq. (A.145) itself has to be equal to (A.146). Substituting this result into Eq. (A.144) and using To derive this result

the definition of the reduced matrix element

((L'S')X 11 [01(space)

x

one

obtains

0,\(spin)l,, 11 (LS)J) L

S

J

2JI + 1

(2LI

+

1) (2SI + 1)

1

A

P

S,

-

x

(L'

01 (space)

L) (S' I I 0,\ (spin)

S).

(A.147)

Exercises

290

In and

special by using

cases one can

(S' 11111 S)

=

set A

=

0

or

1

=

0 in the above formula

JSS, A/2S +I

derive useful formulas

as

(A.148)

given below:

((L'S')J' 11 01(space) 11 (LS)J)

jssl(_I)L-J+J-L' V1-2LI-j,-+1U(SLXl;JL) +I

(L' 11 01(space) 11 L .

x

((L'S')X 11 OX(spin) JLLI

(A.149)

(LS)J)

V TS-,+-, U(LSJA; JS) (S'

Ox (spin)

S).

(A.150) A.2. Derive

Solution.

Eq. (A.19).

Using Eq. (6.18),

we

have

(e. e ) ni (e. r) n2 (ef.,r) n3 rn2 +n3

Y,

Y,

E

BkllBk2l2Bk3l3

2ki+1,,=nj. 2k2+12=n2 2k3+13=n3

(-1)11+12+13-v/'(211

I)T(2172 1) (2K3 +T) [Y11 ( -)

[y12 (' -) Xy12 ('0100 [Y13 0 ) As

was

done in Exercise 6.1

IY12 0

X

Y12 (f9]OO [y13 0 12 13

12 13

0

X

0

X

Y13 ('06'

(see Eq. (6-106)),

)

X

y13 0

0100

(A.151)

we

recouple the product

0

Q12 13; "0 11Y12 (0-)

2K+1 +

Y711 (

)100

-

212

X

1) (213

+

1)

Q12 13; K)

X

Y13 0

)Ir-

X

Yr-(f6)100

Exercises

1[Y12 (P-)

X

X

Y13

0 )I

r-

X

YK M 1 00'

(A.152)

The last step is to combine the two scalar

1YII (10

X

Y11 (0

IRY11 (P-)

X

Y13 (

)100 RY12 ( -)

X

0 )10

[Y12

Y11

X

EELI111101213r-r- [[YL(&)

X

I)JrX

291

products X

Y13

Lf( I&

Y

follows:

YK00100

0 )]KlrX

as

YIs (j

X

Yr-00100 (A.153)

)100,

LL'

given by Eq. (A.75). When one of the angular momenta is zero, the 9j symbol is reduced to the Racah coefficient (see Eq.(6.86)). Using this simplification in the coefficient E and substituting the above results completes the derivation.

where the coefficient E is

A.3. Calculate the matrix element of the orbital

IAjj

angular

momentum

for the correlated Gaussians.

Solution. The matrix element of tween the

gration

lAij

be obtained from that be-

can

generating functions of Table 7.1 or by performin the intein Eq. (A.23) with V(r) being set to unity. The result

over r

is

(fK'L'M'(Ul

i

A

10) 1 IjLjj I fKLM (u, A, x)) 3

BKLBKILI

ff

(

(2v) M-1 detB

2

)

1

*Y, +,q,-Y) c

d2K+L+2K+L'

dMi YLm ( _) YL, m, (o )

AAexp

dA2K+LdX12K-+L'

[q A2 + q1 A/2 + pAYe-e'] i(e x e),, (A.154)

The

integration

over

_ and

o

can

be done

by using the formula

ff de^_d4! YLm( -_)YL,m,(, )*(i(e e),,(e-e')') x

_2 4

1

e=I,eI=1

110111, d,T V '2__Ll+1 (LMIjLjL'M) E Bklv _21+IEW 2k+l=n

Exercises

292

(A.155) Clearly I has to be L I and also L' 1. In order that a possible value L' or IL L'I 2 has to be satisfied. The latter of 1 exists, either L case is obviously impossible because the condition IL L'I < I has to =

=

-

-

be met. Thus

we

equal, otherwise

reach the

the

conclusion that L and L' must be

same

would vanish.

integral

7r(2L

Using

3(L 1) 3(L 7(L2L 47(2L 7F(2L 1)'

3L

QL-I 1; L)

+

QL+1 1; L)

____

-

47r(2L + 1)'

+

-

2+L

U(L-llLl;Ll)=

V:2LL+

U(L+l IM; L1)

2

(A.156) together

with the relation 2k + 2L + 1

BkL-1

=

2k+L we can r

2k

BkLi

Bk-I L+I

Bk-Li (A.157)

show that 11

JJ dM4 YLm( -)YL,Iv,(i )*(i(eJLLI VFL (L In order for the

and

2k+L

+

x

1) (LMly I LM)

integral not

to

vanish,

e'),(e-e)' (A.158)

Bn+I-L

n+I n

+1

2

-

L must be

non-negative

even.

Employing this leads to

Eq. (A.6)

result in a

Eq. (A. 154)

and

compaxing its result with

solution

(fKILIMI (u!, X, X) 11pi, IfKLM(u, A, x))

05LL'1\1L(L + 1) (LMI[tILM) 1 X

-

('Y?71 + 7177) (fKI LM (W, X, X) I fKLM (u, A, x)).

(A.159)

PC

As

a

check of the above

formula,

one

the matrix element of the total orbital 2

7

I:i<j IlLij (see

^11,q)

can

be

Therefore,

Eq. (2.22)).

easily

we

The

done with the

sum-ma

use

of

may

use

angular i n,

this to calculate

momentum

over

i <

LIL

=

j, of .1C (-y?7' +

Eq. (2.15), yielding just

expect that the desired matrix element becomes

z2 Lp.

Exercises

(fK"LfM' (ul A!, x) ILIIfKLM(UA, X)

--`

,

x

JLLI -

fL-(L + 1)

(LM11-ilLM)(fK'LM(WiA iX)IfKLM(UIAIX))-

On the other

hand,

reach the

we can

same

result

293

(A-160)

through the Wigner-

Eckart theorem:

(a'L'M'IL,IaLM) JLLf

:::

JLLI'

(LM IAILM) (aL 11 ,F2L + I

L

11 aL)

(LM 1/ilLM) VIL(L + 1) (aL 11111 aL) ,V -2-L+1

+ 1)(aLMIaLM), JLLI (LM lpILM) VFL-(L

where the labels tions. Here

the

and a' stand for the other labels of the

used the fact that

we

angular

a

(A.161)

momentum of the

L,,

wave

does not

wave

func-

change the magnitude of

function because it is

a

generator

of the rotation group. A.4. Calculate the matrix element of the

the method of Solution. The

spin-orbit potential following

Complement A.I.

integration

over

(fK'LIM" (U A X) I V(I'ri i

7

P is first done in

Eq. (A.23), leading to

-ri 1) IlLij I fKLM (Ui

A X)) 3

00

(,yq +'y

ff

de^-

AA/exp

n)Idr

r2 V(r) e-

47r

IBKLBK"L' ( Cr2

di YLm( -)Ypm, (i )-

(27r)N-2C2 detB

d2K+L+2K'+L' d/\2K+Ld/X/2K+L'

[qA2 + q/A/2 + #AA'e. e] i(e x e%,rii(rv) V

X=0'XI=0 e=I,ef=I

(A.162) Here

v

is the

length of the

vector

v

defined

by Eq. (A.122) and

use

is

made of the formula

f 0"(b

x

r),,&

=

47rrii(ar)(b a

x

a),,,

(A.163)

Exercises

294

can

r), ,

-Nf2i [b

=

V.L3'ir [b

rl

x

v2 term e-2c

The

and

proved by using Eqs. (6.53)

be

which

Yj- (i6)]

x

'i, (rv) is expanded

(6.54)

noting (b

x

I,

done in

as was

-

and

Complement

V

A.I: CO

2 V

exp( 2c) -

1

r

-ii(rv)

2

2n+2

(6cr) C

H2n+3

X

the

Eq. (A.158),

of

use

( 6r) C c

+

2(2n + 3)H2n+l

expansion (A.126) and integrating

the

By using

(V2c)

3

(2c) - ' r n=0 (2n + 3)1

v

n

-rj 1) lij

(

V

K+K+L-1

I:

(7771 + 71,q) C

I

H, (X) H2n+3 (X)

F-x(2n + 3)!

V

+ 2 (2n +

E

32

(2 detB

10 V(jX) e-X2

3) H2n+l (x)

C

I dx

min(K,K) X

with

00

n+I -

n=O

X

4

II fKL(u, A, x))

JLLI 'FL(L+,)(2L+,)(2K+L)!(2K'+L)! BKLBK-L 1

- and

over

obtain

we

(fKf L' (u', A, x) I I V(I'ri

X

(A.164)

-

1

Fk-kKI-kL+2k-I (c, q, qr

BkL. L+2k

k=O

(A.165) In the

when

case

V(r)

=

I

to the matrix element. The function

then becomes

L+2k P

we can

H(K

confirm that

A.5. For

a

=

...,

(X1-i

XK) ---7

matrix, calculate

n

=

0 contributes

Fr2k KI-k L+2k-1 (CI q, q, p, -y, -y)

k, q) H(W

-

k, q) H(L

Eq. (A.165) reduces

given function f (X1, X2

f (X1, X2, where:i

-

term with

only the

to

XK)

+

2k, p) Therefore .

Eq. (A-159).

of the form

=1 TcAx + 6,

XK)7

2

(bl,..., bK),

and A is

a

K

x

K

symmetric

Exercises

,)ni

11==02

ef(Xl,X27---,XK

OX,ni Solution. A solution

(A-166)

7XK::--O*

be obtained with the

can

use

of Leibniz's formula

we

show another way to solve this

+

-+AK

as was

done in A.2. Here

Let

operator L denote

an

...

295

problem.

a L

A,

A2

+

(All

Where

e' 'Cef (xI

7

...

7

7XK)

...

*

AK) =

is

an

auxiliary parameter.

ef (x'+6,

ef(XI

7

...

(A-167)

19XK

(9X2

XI

7XK)

'

7

...

Then

we

have

7XK+IMK)

exp1UXV2 (2 +

W + Ax

11)

-

(A-168)

the above equation in power equal to EK i==l ni. Expanding series of 0, collecting the terms of the Nth power in 0, and putting 0 (i =. 1, K) leads to Xi Let N be

=

...,

(f-Nef(xl

7

...

)XK)

[N 21 =

)

Xj=O .... 7XK=O

N!

E k! (N

(1U ) k( b) N-2k. -

-

k=O

2k)!

2

(A.169) problem of finding a solution to Eq. (A. 166) is thus reduced to a simpler problem of expanding the right-hand side of Eq. (A.169) in are expanded as follows: the Ai's. To this end ( b)N-2k and (WA)k 2 The

(N

( b) N-2k

11! 12!

k

2k)! IK.

(Albl)", (AA) 12 k!

(I)k

AA)

2

-

Mll! M12!

2

7nKK!

(XKbK) 1K,

(All A,2)mll

Mij

x

(2Al2AlA2 )M12

Collecting those obtain

a

solution

...

x

(AKKAK 2)MKK.

terms which have powers of

A,nj A2 n2

(A-170) AK nK

we

Exercises

296

K

ani -e

f(XI,X27

....

9X,ni i2L

XK))x

1=07

...

IXK=O

K

k

(')

E 11 ni!H(mij, Aii)H(li, bi)

2

k=O

i=1

Mij K

XH

H(mij, 2Aij),

(A.171)

j>i=l

where

and

mij's

li's

are

all

non-negative integer and

must

satisfy the

following relations K

K

mij

=

k,

mij +

j>i=l

=

(i

ni

K).

1,

(A. 172)

j=1

A.6. Derive

Eq. (A.93).

Solution. First x

E mji + li

(

2 x

we

note that

(Al) '+Ae-2IpX2_,5X.y YLM 41

M)

(,Axe- .j'8X2_jx.Y) X2v+Ay(,Xl) 2

LM

+

e-12 jax 2-,6X.y A.'X 21/+Ay(,\I) LM PC

+2

(Vxe-2.jpX2_jx`.Y) (VXX

M)

2v+,X

-

AI) YL(M P9M

The differentiation in the second term of the

above equation

(AxX

2v+,\

can

be

right-hand side

performed by using Eq. (6.59)

AO

I

The third term

can

be

reduced, by

means

to

(Vxe- .IpX2_jX.y 2

of the

as

AI) YL(M

2v(2z/ + 2A + I)x 2v+,X-2 YL(M PC M (A.42),

(A.173)

VXX

2v+A

AI) YL(M (ic'

of the

(A.174) gradient formula

Exercises

X2v+X-l e

F+' OX

1

oX2 -,6x.,y

(2v + 2A + 1)

1

-A-+I 2A+1

297

X

YX-1 ('' )4

X

Y' Ml LM

2v[[(- x-Jy)XYX+I( 3)11\Xyl( )ILM (A.175)

By using the angular momentum algebra the equation is reduced to

first term in the round

bracket of the above

[[(-OX

-

JY)

,rL3

X

Y)'-' POD'

X

Y' M] LM

OxC(1A-I;A)YL(A')(:t, ) M

+ Sy

A

U(A-1 I L 1; A r,) C(11; r)Y(X-l LM

2A+lt XYL

X1) M

Jy E U(A

r.)

( O,

-

11 L 1; A

K) C(11; r,) YLM

K

(A.176) where

use

Similarly

is made of

Eq. (A.156)

for

C(l A

-

1;

A)

C(A

-

11; A).

the second term becomes

11(- X-*X YA+'(" )IXX Y1MILM XY(,X1) L M PC M I

yE U(A+I ILI; Ais)C(11; r,)YL(A+1r')(1b, M

The contribution of the first term is

(A.177)

easily obtained by using

Exercises

298

2 e- .l#X2_,5X.y

1

+

02X2 + j2y2 + 2,3dx -,y) e-'2,8X

where the last term

involving

the scalar

2

product

-,5x.y

(A.178)

1

x

-

y

can

be reduced

to

X.

Y Y(Ai) LM

=

,

E

-v -3[x

x

y]oo0'1) LM

U(11 ; 0"0 Ry

X

[X

X

Ily

X

YA-1 4A A

X

Y' MI LM

_X

Ry

X

Y +'P

X

YI(MILM*

-V

3

Y

X

X

1WILM

Y

r.=Al

2,X + I

(A.179)

right-hand side of the above equation appear Eqs. (A.176) and (A.177), respectively. Combining these results we obtain the desired equality (A.93) The two terms of the

Ax

(X

2 Ll +,X

l,3X2_,6x.y

e-2

AI) YL(M

30X2 +,32X4 + j2X2Y2 + 2zj(2i/ + 2A +

2 -2Sx 2v+A-l y e-LPx

I

X

x

):+

TA

I

in

1)) 2

X

1 _

-

20(271 + A)X2

2v+,X-2

2

_,SX.y

LpX2_jX.y

e- 2

V/

YL(M

7F

3

(2y + 2A + 1_ OX2)

EU(A-IlLl;Aiz)C(11;K)YL(A-l)(. c, ) M

Is

'A+I -

2A +I

x

(2y

_

OX2)

I:U(A+IILI;Ar,)C(11;r,,)YL K

M

(A.180)

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