MODERN QUANTUM CHEMISTRY Introduction to Advanced Electronic Structure Theory ATTILA SZABO Laboratory of Chemical Physics National Institutes of Health Bethesda, Maryland NEIL S. OSTLUND Hypercube, Inc. Waterloo, Ontario DOVER PUBLICATIONS, INC. Mineola, New YorkCopyright Copyright © 1982 by Macmillan Publishing Co., Inc. Copyright © 1989 by McGraw-Hill, Ine. Alll rights resers 2d under Pan American and International Copyright Conventions, Published in Canada by General Publishing Company, Ltd.,,30 Lesmilf Road, Don Mills, Toronto, Ontario. : Published in the United Kingdom by Constable and Company, L1d., 3 The Lanchesters, 162-164 Fulham Palace Road, London W6 9ER. Bibliographical Note ‘This Dover edition, first published in 1996, is an unabridged, unaltered republication of the “First Edition, Revised,” originally published by the McGraw-Hill Publishing Com- pany, New York, 1989. The original edition was published by the Macmillan Publishing Company, New York, 1982. Library of Congress Cataloging-in-Publication Data Szabo, Attila, 1947— Modern quantum chemistry : introduction to advanced eleqhronic structure theory / Attila Szabo, Neil S. Ostlund. ! pom, Previously published: Ist ed., rev. New York : McGraw-Hill, 1989. Includes bibliographical references and index. ISBN 0-486-69186-1 (pbk.) j 1. Quantum chemistry. L. Ostlund, Neil S. IL. Title. [QD462.S95 1996] 5A1.2'8—de20 96-0775 crp Manufactured in the United States of America Dover Publications, Inc., 31 East 2nd Street, Mineola, N.Y. 11501TABLE OF CONTENTS Preface to Revised Edition Preface Chapter 1. Mathematical Review Ll 1.2 1.3 Linear Algebra 1.1.1 Three-Dimensional Vector Algebra 2 1.1.2. Matrices 5 1.4.3 Determinants 7 1.1.4 N-Dimensional Complex Vector Spaces 9 1.1.5 Change of Basis /3 1.1.6 The Eigenvalue Problem 1/5 1.1.7 Functions of Matrices 21 Orthogonal Functions, Eigenfunctions, and Operators The Variation Method 1.3.1 The Variation Principle 31 1.3.2 The Linear Variational Problem 33 Notes Further Reading Chapter 2. Many Electron Wave Functions and Operators 21 2.2 The Electronic Problem 2.1.1 Atomic Units 4] 2.1.2. The Born-Oppenheimer Approximation 43 2.1.3. The Antisymmetry or Pauli Exclusion Principle 45 Orbitals, Slater Determinants, and Basis Functions 2.2.1 Spin Orbitals and Spatial Orbitals 46 2.2.2 Hartree Products 47 24 31 38 38 39 46iv MODERN QUANTUM CHEMISTRY 2.3 24 25 2.2.3. Slater Determinants 49 2.24 The Hartree-Fock Approximation 53 2.2.5 The Minimal Basis Hz Model 55 2.2.6 Excited Determinants 58 2.2.7 Form of the Exact Wave Function and Configuration Interaction 60 Operators and Matrix Elements 2.3.1 Minimal Basis H, Matrix Elements 64 2.3.2 Notations for One- and Two-Electron Integrals 67 2.3.3 General Rules for Matrix Elements 68 2.3.4 Derivation of the Rules for Matrix Elements 74 2.3.5 Transition from Spin Orbitals to Spatial Orbitals 8/ 2.3.6 Coulomb and Exchange Integrals 85 2.3.7 Pseudo-Classical Interpretation of Determinantal Energies 87 Second Quantization 2.4.1 Creation and Annihilation Operators and Their Anticommutation Relations 89 242 Second-Quantized Operators and Their Matrix Elements 95 Spin-Adapted Configurations 2.5.1. Spin Operators 97 2.5.2 Restricted Determinants and Spin-Adapted Configurations 100 2.5.3 Unrestricted Determinants 104 Notes Further Reading Chapter 3. The Hartree-Fock Approximation 31 3.2 3.3 3.4 The Hartree-Fock Equations 3.1.1 The Coulomb and Exchange Operators 112 3.1.2. The Fock Operator 11/4 Derivation of the Hartree-Fock Equations 3.2.1 Functional Variation 115 3.2.2. Minimization of the Energy of a Single Determinant 117 3.2.3. The Canonical Hartree-Fock Equations 120 Interpretation of Solutions to the Hartree-Fock Equations 3.3.4 Orbital Energies and Koopmans’ Theorem 123 3.3.2 Brillouin’s Theorem 128 3.3.3. The Hartree-Fock Hamiltoman 130 Restricted Closed-Shell Hartree-Fock: The Roothaan Equations 3.4.1 Closed-Shell Hartree-Fock: Restricted Spin Orbitals 132 3.4.2 Introduction of a Basis: The Roothaan Equations 136 3.4.3 The Charge Density 138 3.4.4 Expression for the Fock Matrix 140 3.4.5 Orthogonalization of the Basis 142 64 89 97 107 107 108 dL 115 123 1313.5 3.6 3.7 3.8 TABLE OF CONTENTS V 3.4.6 The SCF Procedure 145 3.4.7 Expectation Values and Population Analysis 149 Model Calculations on H, and HeH* 3.5.1 The 1s Minimal STO-3G Basis Set 153 35.2 STO-3GH, 159 3.5.3 An SCF Calculation on STO-3G HeH* 168 Polyatomic Basis Sets 3.6.1 Contracted Gaussian Functions 180 3.6.2. Minimal Basis Sets: STO-3G 184 3.6.3 Double Zeta Basis Sets: 4-31G 186 3.6.4 Polarized Basis Sets: 6-31G" and 6-31G** 189 Some Illustrative Closed-Shell Calculations 3.7.1 Total Energies 191 3.7.2 Ionization Potentials 194 3.7.3 Equilibrium Geometries 200 3.7.4 Population Analysis and Dipole Moments 203 Unrestricted Open-Shell Hartree-Fock: The Pople-Nesbet Equations 3.8.1 Open-Shell Hartree Fock: Unrestricted Spin Orbitals 206 3.8.2 Introduction of a Basis: The Pople-Nesbet Equations 2/0 3.8.3 Unrestricted Density Matrices 2/2 3.8.4 Expression for the Fock Matrices 214 3.8.5 Solution of the Unrestricted SCF Equations 2/5 3.8.6 Illustrative Unrestricted Calculations 216 3.8.7 The Dissociation Problem and its Unrestricted Solution 221 Notes Further Reading Chapter 4. Configuration Interaction 4.1 42 43 44 45 46 Multiconfigurational Wave Functions and the Structure of the Full CI Matrix 4.1.1 Intermediate Normalization and an Expression for the Correlation Energy 237 Doubly Excited CI Some Illustrative Calculations Natural Orbitals and the One-Particle Reduced Density Matrix The Multiconfiguration Self-Consistent Field (MCSCF) and Generalized Valence Bond (GVB) Methods Truncated CI and the Size-Consistency Problem 152 190 205 229 229 231 233 242 245 252 258 261Vi MODERN QUANTUM CHEMISTRY Notes Further Reading Chapter 5. Pair and Coupled-Pair Theories 5.1. The Independent Electron Pair Approxunation (IEPA) 5.1.1 Invariance under Unitary Transformations: An Example 277 512 Some Illustrative Calculations 284 5.2 Coupled-Pair Theories 5.2.1 The Coupled Cluster Approximation (CCA) 287 5.2.2. The Cluster Expansion of the Wave Func 290 5.2.3. Linear CCA and the Coupled Electron Pair Approximauon (CEPA) 292 5.2.4 Some Illustrative Calculations 296 5.3. Many-Electron Theories with Single Particle Hamiltonians 5.3.1 The Relaxation Energy via Cl, IEPA, CCA, and CEPA 303 5.3.2 The Resonance Energy of Polyenes in Hiickel Theory 309 Notes Further Reading Chapter 6. Many-Body Perturbation Theory 6.1 Rayleigh-Schrédinger (RS) Perturbation Theory *6.2 Diagrammatic Representation of RS Perturbation Theory 6.2.1 Diagrammatic Perturbation Theory for 2 States 327 62.2 Diagrammauc Perturbation Theory for N States 335 6.2.3 Summation of Diagrams 336 6.3 Orbital Perturbation Theory: One-Particle Perturbations *6.4 Diagrammatic Representation of Orbital Perturbation Theory 6.5 Perturbation Expansion of the Correlation Energy 6.6 The N-Dependence of the RS Perturbation Expansion “6.7 Diagrammatic Representation of the Perturbation Expansion of the Correlation Energy 671 Hugenholtz Diagrams 356 672 Goldstone Diagrams 362 673 Summation of Diagrams 368 6.7.4 What Is the Linked Cluster Theorem? 369 6.8 Some Illustrative Calculations Notes Further Reading 269 269 271 272 286 297 318 319 320 322 327 338 348 350 354 356 370 378 379TABLE OF CONTENTS Vii Chapter 7. The One-Particle Many-Body Green’s Function 7.1 Green’s Functions in Single Particle Systems 7.2 The One-Particle Many-Body Green’s Function 7.21 The Self-Energy 389 7.2.2. The Solution of the Dyson Equation 391 7.3 Application of the Formalism to H, and HeH* 7.4 Perturbation Theory and the Green’s Function Method 7.5 Some Illustrative Calculations Notes Further Reading Appendix A, Integral Evaluation with 1s Primitive Gaussians Appendix B. Two-Electron Self-Consistent-Field Program Appendix C. Analytic Derivative Methods and Geometry Optimization by M.C. Zerner Appendix D. Molecular Integrals for H, as a Function of Bond Length Index 380 381 387 392 398 405 409 410 417 437 459 461Szeretettel a sziileimnek AS To my wonderful father and the memory of my dear mother NSOPREFACE TO REVISED EDITION This revised edition differs from its predecessor essentially in three ways. First, we have included an appendix describing the important recent de- velopments that have made the efficient generation of equilibrium geo- metries almost routine. We are fortunate that M. Zerner agreed to write this since our own recent interests have been channeled in other directions. Second, numerous minor but annoying errors have been corrected. For most of these we are indebted to K. Ohno, T. Sakai and Y. Mochizuki who detected them in the course of preparing the Japanese translation which has recently been published by Tokyo University Pres. Finally, we have updated the Further Reading sections of all the chapters. We are extremely pleased by the many favorable comments we have received about our book and we hope that the next generation of readers will find this edition useful. ATTILA SZABO NEIL S. OSTLUNDPREFACE The aim of this graduate textbook is to present and explain, at other than a superficial level, modern ab initio approaches to the calculation of the electronic structure and properties of molecules. The first three chapters contain introductory material culminating in a thorough discussion of the Hartree-Fock approximation, The remaining four chapters describe a variety of more sophisticated approaches, which improve upon this approximation. We have strived to make advanced :opics understandable to the be- ginning graduate student. Our goal was to teach more than cocktail party jargon; we wanted to give insight into the nature and validity of a variety of approximate formalisms and improve the reader’s problem-solving skills. Needless to say, a book of this size cannot cover all of quantum chemistry; it would be easy to write down a long list of important topics which we have not covered. Nevertheless, we believe that anyone who has mastered the material in this book will have a solid foundation to build upon, and will be able to appreciate most research papers and seminars dealing with electronic structure theory and its applications. The origins of this book go back to our student days when we were trying to understand a variety of quantum chemical formalisms that at first glance appeared to be extremely complicated. We found that by applying such formalisms to simple, analytically tractable, model systems we not only got a feeling as to what was involved in performing actual calculations but also gained insight into the interrelationships among different approximation schemes. The models we used then, and ones we devised or learned sub- sequently, play an important role in the pedagogical approach we adopt in this book. The writing began in 1976 when we jointly taught a special topics course at Indiana University. The manuscript gradually evolved in response to the needs and reactions of students enrolled in a second-semester quantumxii MODERN QUANTUM CHEMISTRY chemistry course we taught some five times at both Indiana University and the University of Arkansas. Animportant feature of this book is that over 150 exercises are embedded in the body of the text. These problems were designed to help the reader acquire a working knowledge of the material. The level of difficulty has been kept reasonably constant by breaking up the more complicated ones into manageable parts. Much of the value of this book will be missed if the exercises are ignored. In the following, we briefly describe some of the highlights of the seven chapters. Chapter 1 reviews the mathematics (mostly matrix algebra) re- quired for the rest of the book. It is self-contained and suited for self-study. Its presence in this book is dictated by the deficiency in mathematics of most chemistry graduate students. The pedagogical strategy we use here, and in much of the book, is to begin with a simple example that illustrates most of the essential ideas and then gradually generalize the formalism to handle more complicated situations. Chapter 2 introduces the basic techniques, ideas, and notations of quantum chemistry. A preview of Hartree-Fock theory and configuration interaction is used to motivate the study of Slater determinants and the evaluation of matrix elements between such determinants. A simple model system (minimal basis H,) is introduced to illustrate the development. This model and its many-body generalization (N independent H, molecules) reappear in all subsequent chapters to illuminate the formalism. Although not essential for the comprehension of the rest of the book, we also present here a Self-contained discussion of second quantization. Chapter 3 contains a thorough discussion of the Hartree-Fock approx- imation. A unique feature of this chapter is a detailed illustration of the computational aspects of the self-consistent-field procedure for minimal basis HeH*. Using the output of a simple computer program, listed in Appendix B, the reader is led iteration-by-iteration through an ab initio calculation. This chapter also describes the results of Hartree-Fock calcula- tions on a standard set of simple molecules using basis sets of increasing sophistication. We performed most of these calculations ourselves, and in later chapters we use these same molecules and basis sets to show how the Hartree-Fock results are altered when more sophisticated approaches are used. Thus we illustrate the influence of both the quality of the one-electron basis set and the sophistication of the quantum chemical method on cal- culated results. In this way we hope to give the reader a feeling for the kind of accuracy that can be expected from a particular calculation. Chapter 4 discusses configuration interaction (CI) and is the first of the four chapters that deal with approaches incorporating electron correlation. One-electron density matrices, natural orbitals. the multiconfiguration self- consistent-field approximation, and the generalized valence bond method arePREFACE Xiii discussed from an elementary point of view. The size-consistency problem associated with truncated CI is illustrated using a model consisting of N independent hydrogen molecules. This example highlights the need for so-called many-body approaches, which do not suffer from this deficiency, that are discussed in subsequent chapters. Chapter 5 describes the independent electron pair approximation and a variety of more sophisticated approaches that incorporate coupling be- tween pairs. Since this chapter contains some of the most advanced material in the book, many illustrative examples are included. In the second half of the chapter, as a pedagogical device, we consider the application of many- electron approaches to an N-electron system described by a Hamiltonian containing only single particle interactions. This problem can be solved exactly in an elementary way. However, by seeing how “high-powered” approaches work in such a simple context. the student can gain insight into the nature of these approximations. Chapter 6 considers the perturbative approach to the calculation of the correlation energy of many-electron systems. A novel pedagogical approach allows the reader to acquire a working knowledge of diagrammatic pertur- bation theory surprisingly quickly. Although the chapter is organized so that the sections on diagrams (which are starred) can be skipped without loss of continuity, we find that the diagrammatic approach is fun to teach and is extremely well received by students. Chapter 7 contains a brief introduction to the use of the one-particle many-body Green’s function in quantum chemistry. Our scope is restricted to discussing ionization potentials and electron affinities. The chapter is directed towards a reader having no knowledge of second quantization or Green’s functions, even in a simple context. This book is largely self-contained and, in principle, requires no pre- requisite other than a solid undergraduate physical chemistry course. How- ever, exposure to quantum chemistry at the level of the text by I. N. Levine (Quantum Chemistry, Allyn and Bacon) will definitely enhance the student’s appreciation of the subject material. We would normally expect the present text to be used for the second semester of a two-semester sequence on quan- tum chemistry. It is also suitable for a special topics course. There is probably too much material in the book to be taught in-depth in a single semester. For students with average preparation, we suggest covering the first four chapters and then discussing any one of the last three, which are essentially independent. Our preferred choice is Chapter 6. For an exceptionally well- prepared class, the major fraction of the semester could be spent on the last four chapters. We have found that a course based on this text can be enriched in a number of ways. For example, it is extremely helpful for students to perform their own numerical calculations using, say, the Gaussian 80 system of programs. In addition, recent papers on the applications of