Hjem

Preface to the Third Edition xvii Extract from the Preface to the Second Edition xix Extracts from the Preface to the First Edition xxiii Foreword to the First Edition xxv Mathematical Symbols xxvii Abbreviations xxxiii 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 Phase Transitions and Helicoidal Structures 603 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 vmm 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 Vmm 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