Electronic Structure and Properties of Transition Metal Compounds

Isaac B. Bersuker, PhD, DSc, was a Senior Research Scientist and Professor of Theoretical Chemistry, presently affiliated with the Oden Institute of the University of Texas at Austin. He is a member of the Academy of Sciences of Moldova and the recipient of numerous awards, including the Medal of Honor (Republic of Moldova), the David Ben-Gurion Medal (Be’er Sheva University), and the Chugaev Medal (Russian Academy of Sciences). Dr. Bersuker has published 425 peer-reviewed papers, authored 15 books and 35 major reviews, and supervised more than 50 PhD. Based on AI investigation, Special Institute ScholarGPS revealed that Dr. Bersuker is a 0.5% Top Scholar worldwide (Wikipedia). Yang Liu, PhD, is an Associate Professor in the School of Chemistry and Chemical Engineering at Harbin Institute of Technology (China). She obtained her PhD from Jilin University (China), and conducted her postdoctoral research with Prof. Issac B. Bersuker and Prof. James E. Boggs at the University of Texas at Austin (USA) and with Prof. Dong-Sheng Yang at the University of Kentucky (USA). She has broad research interests in theoretical and computational chemistry, photochemistry, and catalytic chemistry, particularly vibronic interaction and symmetry-related research topics for molecules and solid materials with applications in physics, chemistry, environment, and biology. She has published more than 60 scientific papers and granted several patents.

• Preface to the Third Edition xviiExtract from the Preface to the Second Edition xixExtracts from the Preface to the First Edition xxiiiForeword to the First Edition xxvMathematical Symbols xxviiAbbreviations xxxiii1 Introduction: Subject and Methods 11.1 Objectives 11.2 Definitions of Chemical Bonding and Transition Metal Coordination System 81.3 The Schrödinger Equation 13Summary Notes 16References 172 Atomic States 192.1 One-Electron States 192.2 Multielectron States: Energy Terms 38Summary Notes 54Questions 55Exercises and Problems 55References 563 Symmetry Ideas and Group-Theoretical Description 593.1 Symmetry Transformations and Matrices 603.2 Groups of Symmetry Transformations 663.3 Classification of Point Groups 673.4 Representations of Groups and Matrices of Representations 713.5 Classification of Molecular Terms and Vibrations, Selection Rules, and The Wigner–Eckart Theorem 783.6 Construction of Symmetrized Molecular Orbitals and Normal Vibrations 833.7 The Notion of Double Groups 92Summary Notes 93Exercises and Problems 94References 954 Crystal Field Theory 974.1 Introduction 974.2 Splitting of the Energy Levels of One d Electron in Ligand Fields 994.3 Several d Electrons 1144.4 f-Electron Term Splitting 1344.5 Crystal Field Parameters and Extrastabilization Energy 1374.6 Limits of Applicability of Crystal Field Theory 141Summary Notes 143Questions 144Exercises and Problems 145References 1465 Molecular Orbitals and Related Description of Electronic Structure 1495.1 Basic Ideas of the MO LCAO Method 1495.2 Charge Distribution and Bonding in the MO LCAO Method. The Case of Weak Covalency 1615.3 Methods of Calculation of MO Energies and LCAO Coefficients 1735.4 Density Functional Theory 1925.5 Electronic Structure Calculations for Large Polyatomic Systems 2095.6 Comparison of Methods and Computer Programs 232Summary Notes 239Exercises and Problems 240References 2416 Electronic Structure and Chemical Bonding 2496.1 Classification of Chemical Bonds by Electronic Structure and Role of d and f Electrons in Coordination Bonding 2496.2 Qualitative Aspects and Electronic Configurations 2586.3 Ligand Bonding 2676.4 Energies, Geometries, and Charge Distributions 3036.5 Relativistic Effects 315Summary Notes 332Exercises and Problems 333References 3357 Vibronic Coupling in Formation, Deformation, and Transformation of Polyatomic Systems. The Jahn–Teller Effects 3437.1 Molecular Vibrations 3447.2 Vibronic Coupling 3567.3 The Jahn–Teller Effects 3637.4 Pseudo-Jahn–Teller Effect and the Two-Level Paradigm 396Summary Notes 415Exercises and Problems 416References 4178 Electronic Structure Investigated by Physical Methods 4218.1 Band Shapes of Electronic Spectra 4228.2 d–d, Charge Transfer, Infrared, and Raman Spectra 4368.3 X-ray and Ultraviolet Photoelectron Spectra; EXAFS 4578.4 Magnetic Properrties 4748.5 Gamma-resonance Spectroscopy 5038.6 Electron Charge and Spin Density distribution in Diffraction Method 514Summary Notes 526Exercises and Problems 528References 5329 Stereochemistry and Crystal Chemistry 5399.1 Definitions. Semiclassical Approaches 5399.2 Vibronic Effects in Stereochemistry 5559.3 Mutual Influence of Ligands 5809.4 Crystal Stereochemistry 591Phase Transitions and Helicoidal Structures 603Summary Notes 610Exercises and Problems 612References 61310 Charge Transfer, Redox Properties, and Electron-conformational Effects 61910.1 Electron Transfer and Charge Transfer by Coordination 61910.2 Electron Transfer in Mixed-Valence Compounds 63310.3 Electron-Conformational Effects In Biological Systems 652Summary Notes 661Exercises and Problems 662References 66311 Reactivity and Catalytic Action 66711.1 Electronic Factors in Reactivity 66711.2 Electronic Control of Chemical Activation Via Vibronic Coupling 68211.3 Direct Computation of Energy Barriers of Chemical Reactions 706Summary Notes 733Questions and Problems 734References 736Appendix 1. Tables of Characters of Irreducible Representations of Most Usable Symmetry Point Groups and Direct Products of Some Representations 741Appendix 2. General Expressions for the Matrix Element vmm of Perturbation of the States of one d Electron in Crystal Fields of Arbitrary Symmetry 747Appendix 3. Calculation of the Destabilization and Splitting of the States of One d Electron in Crystal Fields of Different Symmetries 751Appendix 4. Matrix Elements of Crystal Field Perturbation of a Two-Electron Term F(nd)2, Vij , i, j = 1,2, …, 7 Expressed by One-Electron Matrix Elements Vmm Given in Appendix 2 757Appendix 5. Matrix Elements of Crystal Field Perturbation of f-Electron States 759Answers and Solutions 763Subject Index 817