Preface to the Third Editionxvii
Extract from the Preface to the Second Editionxix
Extracts from the Preface to the First Edition xxiii
Foreword to the First Editionxxv
Mathematical Symbolsxxvii
Abbreviationsxxxiii
1 Introduction: Subject and Methods 1
1.1 Objectives 1
1.2 Definitions of Chemical Bonding and Transition Metal Coordination System 8
1.3 The Schrödinger Equation 13
Summary Notes 16
References 17
2 Atomic States 19
2.1 One-Electron States 19
2.2 Multielectron States: Energy Terms 38
Summary Notes 54
Questions 55
Exercises and Problems 55
References 56
3 Symmetry Ideas and Group-Theoretical Description 59
3.1 Symmetry Transformations and Matrices 60
3.2 Groups of Symmetry Transformations 66
3.3 Classification of Point Groups 67
3.4 Representations of Groups and Matrices of Representations 71
3.5 Classification of Molecular Terms and Vibrations, Selection Rules, and The Wigner-Eckart Theorem
78
3.6 Construction of Symmetrized Molecular Orbitals and Normal Vibrations 83
3.7 The Notion of Double Groups 92
Summary Notes 93
Exercises and Problems 94
References 95
4 Crystal Field Theory 97
4.1 Introduction 97
4.2 Splitting of the Energy Levels of One d Electron in Ligand Fields 99
4.3 Several d Electrons 114
4.4 f-Electron Term Splitting 134
4.5 Crystal Field Parameters and Extrastabilization Energy 137
4.6 Limits of Applicability of Crystal Field Theory 141
Summary Notes 143
Questions 144
Exercises and Problems 145
References 146
5 Molecular Orbitals and Related Description of Electronic Structure 149
5.1 Basic Ideas of the MO LCAO Method 149
5.2 Charge Distribution and Bonding in the MO LCAO Method. The Case of Weak Covalency 161
5.3 Methods of Calculation of MO Energies and LCAO Coefficients 173
5.4 Density Functional Theory 192
5.5 Electronic Structure Calculations for Large Polyatomic Systems 209
5.6 Comparison of Methods and Computer Programs 232
Summary Notes 239
Exercises and Problems 240
References 241
6 Electronic Structure and Chemical Bonding 249
6.1 Classification of Chemical Bonds by Electronic Structure and Role of d and f Electrons in Coordination Bonding 249
6.2 Qualitative Aspects and Electronic Configurations 258
6.3 Ligand Bonding 267
6.4 Energies, Geometries, and Charge Distributions 303
6.5 Relativistic Effects 315
Summary Notes 332
Exercises and Problems 333
References 335
7 Vibronic Coupling in Formation, Deformation, and Transformation of Polyatomic Systems. The Jahn-Teller Effects 343
7.1 Molecular Vibrations 344
7.2 Vibronic Coupling 356
7.3 The Jahn-Teller Effects 363
7.4 Pseudo-Jahn-Teller Effect and the Two-Level Paradigm 396
Summary Notes 415
Exercises and Problems 416
References 417
8 Electronic Structure Investigated by Physical Methods 421
8.1 Band Shapes of Electronic Spectra 422
8.2 d-d, Charge Transfer, Infrared, and Raman Spectra 436
8.3 X-ray and Ultraviolet Photoelectron Spectra; EXAFS 457
8.4 Magnetic Properrties 474
8.5 Gamma-resonance Spectroscopy 503
8.6 Electron Charge and Spin Density distribution in Diffraction Method 514
Summary Notes 526
Exercises and Problems 528
References 532
9 Stereochemistry and Crystal Chemistry 539
9.1 Definitions. Semiclassical Approaches 539
9.2 Vibronic Effects in Stereochemistry 555
9.3 Mutual Influence of Ligands 580
9.4 Crystal Stereochemistry 591
Summary Notes 610
Exercises and Problems 612
References 613
10 Charge Transfer, Redox Properties, and Electron-conformational Effects 619
10.1 Electron Transfer and Charge Transfer by Coordination 619
10.2 Electron Transfer in Mixed-Valence Compounds 633
10.3 Electron-Conformational Effects In Biological Systems 652
Summary Notes 661
Exercises and Problems 662
References 663
11 Reactivity and Catalytic Action 667
11.1 Electronic Factors in Reactivity 667
11.2 Electronic Control of Chemical Activation Via Vibronic Coupling 682
11.3 Direct Computation of Energy Barriers of Chemical Reactions 706
Summary Notes 733
Questions and Problems 734
References 736
Appendix 1. Tables of Characters of Irreducible Representations of Most Usable Symmetry Point Groups
and Direct Products of Some Representations 741
Appendix 2. General Expressions for the Matrix Element v mm of Perturbation of the States of one d
Electron in Crystal Fields of Arbitrary Symmetry 747
Appendix 3. Calculation of the Destabilization and Splitting of the States of One d Electron in Crystal
Fields of Different Symmetries 751
Appendix 4. Matrix Elements of Crystal Field Perturbation of a Two-Electron Term F(nd) 2 ,V ij , i, j = 1,2, ..., 7 Expressed by One-Electron Matrix Elements V mm Given in Appendix 2 757
Appendix 5. Matrix Elements of Crystal Field Perturbation of f-Electron States 759
Answers and Solutions 763
Subject Index 817
