Electronic Structure and Properties of Transition Metal Compounds: Theory and Applications

by Isaac B. Bersuker, Yang Liu

Overview

Presents the latest achievements in the theory of electronic structure and properties of transition metal coordination compounds with applications to a range of chemical and physical problems

Electronic Structure and Properties of Transition Metal Compounds offers a detailed and authoritative account of the theory of electronic structure and the properties of transition metal compounds with applications to various chemical and physical problems.

The fully updated third edition incorporates recent developments and methods in the field, including new coverage of methods of ab initio calculations of the electronic structure of coordination compounds and the application of vibronic coupling and the Jahn-Teller effect to solve coordination chemistry problems. Revised chapters provide up-to-date views on reactivity, chemical activation, and catalysis. New and expanded questions, exercises, and problems in each chapter are supported by new problem-solving examples, illustrations, graphic presentations, and references.

Designed to be intelligible to advanced students, researchers, and instructors, Electronic Structure and Properties of Transition Metal Compounds:

• Provides thorough coverage of the theory underlying the electronic structure and properties of transition metal compounds, including the physical methods of their investigation
• Helps readers understand the origin of observable properties in transition metal compounds and choose a suitable method of their investigation
• Contains numerous problems with solutions and illustrative examples demonstrating the application of the theory to solving specific chemical and physical problems
• Presents a generalized view of the modern state of the field, beginning from the main ideas of quantum chemistry and atomic states to applications to various chemical and physical problems
• Features novel problems never fully considered in books on coordination chemistry, such as relativistic effects in bonding, optical band shapes, and electron transfer in mixed-valence compounds

Electronic Structure and Properties of Transition Metal Compounds: Theory and Applications, Third Edition is an excellent textbook for graduate and advanced undergraduate chemistry students, as well as a useful reference for inorganic, bioinorganic, coordination, organometallic, and physical chemists and industrial and academic researchers working in catalysis, organic synthesis, materials science, and physical methods of investigation.

Product Details

ISBN-13:	9781394178919
Publisher:	Wiley
Publication date:	03/25/2025
Sold by:	JOHN WILEY & SONS
Format:	eBook
Pages:	864
File size:	21 MB
Note:	This product may take a few minutes to download.

About the Author

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.

Table of Contents

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 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