
Electronic Structure and Properties of Transition Metal Compounds
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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.
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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.
Inhalt
- Cover
- Title Page
- Copyright Page
- ?Contents
- Preface to the Third Edition
- Extract from the Preface to the Second Edition
- Extracts from the Preface to the First Edition
- Foreword to the First Edition
- Mathematical Symbols
- Abbreviations
- Chapter 1 Introduction: Subject and Methods
- 1.1 Objectives
- 1.1.1 Molecular Engineering and Intuitive Guesswork
- 1.1.2 Main Objectives of This Book in Comparison with Other Sources
- 1.2 Definitions of Chemical Bonding and Transition Metal Coordination System
- 1.2.1 Chemical Bonding as an Electronic Phenomenon
- 1.2.2 Definition of Coordination System
- 1.3 The Schrödinger Equation
- 1.3.1 Formulation
- 1.3.2 Role of Approximations
- Summary Notes
- References
- Chapter 2 Atomic States
- 2.1 One-Electron States
- 2.1.1 Angular and Radial Functions
- 2.1.2 Orbital Overlaps: Hybridized Functions
- 2.1.3 Spin-Orbital Interaction
- 2.1.4 Relativistic Atomic Functions
- 2.2 Multielectron States: Energy Terms
- 2.2.1 Electronic Configurations and Terms
- 2.2.2 Multielectron Wavefunctions
- 2.2.3 Slater-Condon and Racah Parameters
- 2.2.4 The Hartree-Fock Method
- Summary Notes
- Questions
- Exercises and Problems
- References
- Chapter 3 Symmetry Ideas and Group-Theoretical Description
- 3.1 Symmetry Transformations and Matrices
- 3.2 Groups of Symmetry Transformations
- 3.3 Classification of Point Groups
- Example 3.1. The Symmetry Group of an Octahedral Oh System and Its Classes
- 3.4 Representations of Groups and Matrices of Representations
- Example 3.2. The Rules of IrReps and Characters in C4v Point Group
- 3.5 Classification of Molecular Terms and Vibrations, Selection Rules, and The Wigner-Eckart Theorem
- Example 3.3. Energy Terms of Electronic Configuration e2
- 3.6 Construction of Symmetrized Molecular Orbitals and Normal Vibrations
- Example 3.4. Construction of Eg-Symmetry-Adapted s MOs for Octahedral Oh Systems
- Example 3.5. Construction of T2g-Symmetry-Adapted p MOs for Octahedral Oh Systems
- Example 3.6. Normal Coordinates of a Regular Triangular Molecule X3
- 3.7 The Notion of Double Groups
- Summary Notes
- Exercises and Problems
- References
- Chapter 4 Crystal Field Theory
- 4.1 Introduction
- 4.1.1 Brief History
- 4.1.2 Main Assumptions
- 4.2 Splitting of the Energy Levels of One d Electron in Ligand Fields
- 4.2.1 Qualitative Aspects and Visual Interpretation
- 4.2.2 Calculation of the Splitting Magnitude
- Example 4.1. Splitting of a d-Electron Term in Octahedral Crystal Fields
- 4.2.3 Group-Theoretical Analysis
- 4.3 Several d Electrons
- 4.3.1 Case of a Weak Field
- 4.3.2 Strong Crystal Fields and Low- and High-Spin Complexes
- Example 4.2. High-Spin and Low-Spin Octahedral Complexes of Iron
- 4.3.3 Energy Terms of Strong-Field Configurations
- 4.3.4 Arbitrary Ligand Fields and Tanabe-Sugano Diagrams
- 4.4 f-Electron Term Splitting
- 4.5 Crystal Field Parameters and Extrastabilization Energy
- 4.6 Limits of Applicability of Crystal Field Theory
- Summary Notes
- Questions
- Exercises and Problems
- References
- Chapter 5 Molecular Orbitals and Related Description of Electronic Structure
- 5.1 Basic Ideas of the MO LCAO Method
- 5.1.1 Main Assumptions
- 5.1.2 Secular Equation
- 5.1.3 Classification by Symmetry
- 5.1.4 Symmetrized Orbitals
- 5.1.5 Simplification of the Secular Equation
- 5.1.6 A Short Note on Band Structure of Transition Metal Solids
- 5.2 Charge Distribution and Bonding in the MO LCAO Method. The Case of Weak Covalency
- 5.2.1 Atomic Charges and Bond Orders
- Example 5.1. Shortcomings of Mulliken's Definition of Atomic Charges in Molecules
- 5.2.2 Bonding, Nonbonding, and Antibonding Orbitals
- 5.2.3 Case of Weak Covalency
- 5.2.4 Angular Overlap Model
- 5.3 Methods of Calculation of MO Energies and LCAO Coefficients
- 5.3.1 SCF MO LCAO Approximation
- 5.3.2 Electron Correlation Effects
- 5.3.3 Basis Sets and Pseudopotentials
- EXAMPLE 5.2 Calculate the CuF2 Molecule Using Hartree-Fock and MP2 Methods
- Example 5.3. Calculate the Absorption and Emission spectra of [Cr(ddpd)2]3+ (ddpd = N,N -dimethyl- N,N -dipyridin-2-ylpyridine-2,6-diamine) using CASSCF and CASPT2 Methods
- 5.4 Density Functional Theory
- 5.4.1 Hohenberg-Kohn (HK) Method
- 5.4.2 Exchange-Correlation Functional
- 5.4.3 Time-Dependent DFT (TD-DFT)
- 5.4.4 Density-Functional Tight Binding (DFTB)
- Example 5.4. Calculation of ZnCl2 by the DFT Method
- Example 5.5. DFT Calculation of the Energy of Absorption of the O2 on the Surface of CoN4-ZnN4/C Material
- 5.5 Electronic Structure Calculations for Large Polyatomic Systems
- 5.5.1 Fragmentary Calculations
- 5.5.2 Molecular Mechanics
- Example 5.6. Application of Molecular Modeling to Transition Metal Complexes with Macrocycles
- 5.5.3 Combined Quantum/Classical (QM/MM) Methods
- EXAMPLE 5.7 Oxidative Addition of H2 to Pt(P(t-Bu)3)2 Treated by ONIOM Version ofQM/MM Methods
- Example 5.8. Iron Picket-Fence Porphyrin Treated by the QM/MM Method with Charge Transfer (QM/MM/CT)
- 5.5.4 Machine Learning Force Fields (MLFF) Method
- 5.6 Comparison of Methods and Computer Programs
- Summary Notes
- Exercises and Problems
- References
- Chapter 6 Electronic Structure and Chemical Bonding
- 6.1 Classification of Chemical Bonds by Electronic Structure and Role of d and f Electrons in Coordination Bonding
- 6.1.1 Criticism of the Genealogical Classification
- 6.1.2 Classification by Electronic Structure and Properties
- 6.1.3 Features of Coordination Bonds
- 6.1.4 Coordination Bonding by Pre- and Post-transition Elements
- 6.2 Qualitative Aspects and Electronic Configurations
- 6.2.1 Most Probable MO Schemes
- 6.2.2 Electronic Configurations in Low- and High-Spin Complexes
- 6.2.3 Covalence Electrons and Ionization Potentials
- 6.3 Ligand Bonding
- 6.3.1 General Considerations: Multiorbital Bonds
- 6.3.2 Mono-orbital Bonds: Coordination of NH3 and H2O
- Example 6.1. Ab Initio Numerical SCF CI Calculations of the Electronic Structure of Mono-orbital Bonds: Ni(H2O)n and Ni(PH3)n, n =1, 2
- 6.3.3 Diorbital Bonds: Coordination of the N2 Molecule
- Example 6.2. Electronic Structure and Bonding in FeN2
- 6.3.4 Coordination of Carbon Monoxide
- Example 6.3. Bonding and Charge Transfer in the Pt-CO Complex
- Example 6.4. Bonding in M-CO with M = Cr, Fe, Co, Ni
- Example 6.5. Bonding in Sc-CO, Ni-CO, and Ni(CO)2
- 6.3.5 s + p Bonding
- Example 6.6. Electronic Structure of Transition Metal Hexacarbonils M(CO)6
- 6.3.6 CO Bonding on Surfaces
- 6.3.7 Bonding of NO
- Example 6.7. Coordination of NO on the Ni(111) Surface
- 6.3.8 Coordination of C2H4
- Example 6.8. Ethylene Bonding to Transition Metal Centers
- Example 6.9. Ethylene Bonding in PtCl3(C2H4)- and PdCl3(C2H4)-
- 6.3.9 Metal-Metal Bonds and Bridging Ligands
- Example 6.10. Multiple Metal-Metal Bonds in [Re2Cl8]2- and [Mo2Cl8]4-
- 6.4 Energies, Geometries, and Charge Distributions
- 6.4.1 Ionization Energies
- Example 6.11. Ab Initio Calculations of Ni(C3H5)2
- 6.4.2 Total and Bonding Energies, Geometries, and Other Properties
- 6.5 Relativistic Effects
- 6.5.1 Relativistic Approaches
- 6.5.2 Orbital Contraction and Valence Activity
- Example 6.12. Relativistic Effects in Catalytic Activity of Pt and Pd Complexes
- 6.5.3 Bond Lengths, Bond Energies, and Vibrational Frequencies
- Example 6.13. Relativistic Effects in Metal Hydrides
- 6.5.4 Correlation Between Spin-Orbital Splitting and Bonding
- Example 6.14. Relativistic Semiempirical Calculation of PtCl6 2-
- 6.5.5 Other Relativistic Effects
- Summary Notes
- Exercises and Problems
- References
- Chapter 7 Vibronic Coupling in Formation, Deformation, and Transformation of Polyatomic Systems. The Jahn-Teller Effects
- 7.1 Molecular Vibrations
- 7.1.1 Adiabatic Approximation
- 7.1.2 Normal Coordinates and Harmonic Vibrations
- 7.1.3 Special Features of Vibrations of Coordination Compounds
- 7.2 Vibronic Coupling
- 7.2.1 Vibronic Constants
- 7.2.2 Orbital Vibronic Constants
- Example 7.1. Vibronic MO Description of Electronic Structure of N2 and CO
- 7.3 The Jahn-Teller Effects
- 7.3.1 The Jahn-Teller Theorem
- 7.3.2 The Pseudo-Jahn-Teller Effect
- 7.3.3 Hidden-Jahn-Teller and Hidden Pseudo-Jahn-Teller Effects. Four Modifications of Jahn-Teller Effects
- Example 7.2. Hidden-JTE Origin of Instability of the High-Symmetry Configuration of the Ozone Molecule
- 7.3.4 Configurations with h-PJTE and Spin Crossover
- Example 7.3. Hidden-PJTE Origin of Instability of the High-Symmetry Configuration of the CuF3 Molecule
- 7.3.5 The Renner-Teller Effect
- 7.3.6 The Jahn-Teller Effect in a Twofold-Degenerate Electronic State
- 7.3.7 Threefold-Degenerate Electronic States
- 7.4 Pseudo-Jahn-Teller Effect and the Two-Level Paradigm
- 7.4.1 Pseudo-Jahn-Teller (PJT) Instability
- 7.4.2 Uniqueness of the Vibronic Mechanism of Structural Configuration Instability. The Two-Level Paradigm
- Example 7.4. Numerical Confirmation of the Pseudo-Jahn-Teller Origin of Instability of High-Symmetry Configurations of Simple Molecules
- Example 7.5. Numerical Calculations Confirming the Pseudo-Jahn-Teller Origin of Configuration Instability of Coordination Systems
- 7.4.3 Further Insight into the Pseudo-JTE and Hidden JTE
- Example 7.7. Why Some ML2 Molecules (M = Ca, Sr, Ba
- L = H, F, Cl, Br) are Bent While Others Are Linear?
- Example 7.8. Direct Applications of the Jahn-Teller Effects in Materials Science and Engineering
- Example 7.6. Comparison of Covalence Versus Polarization Contributions to PJT Instability
- Summary Notes
- Exercises and Problems
- References
- Chapter 8 Electronic Structure Investigated by Physical Methods
- 8.1 Band Shapes of Electronic Spectra
- 8.1.1 Qualitative Interpretation of Vibrational Broadening
- Example 8.1. Broad and Narrow Bands in Light Absorption and Emission by Transition Metal Complexes
- 8.1.2 Theory of Absorption Band Shapes
- 8.1.3 Band Shapes of Electronic Transitions Between Nondegenerate States
- Zero-Phonon Lines
- 8.1.4 Types of Electronic Transitions on Intensity
- Example 8.2. Selection Rules for Polarized Light Absorption by the PtCl4 2- Complex
- 8.2 d-d, Charge Transfer, Infrared, and Raman Spectra
- 8.2.1 Origin and Special Features of d-d Transitions
- Example 8.3. d-d Transitions in the Absorption Spectrum of Mn(H2O)6 2+
- Example 8.4. Temperature-Dependent Absorption Spectra of K2NaCrF6 and Emerald
- 8.2.2 Spectrochemical and Nephelauxetic Series
- 8.2.3 Charge Transfer Spectra
- Example 8.5. Some Ligand Metal or Metal Ligand Charge Transfer Spectra
- 8.2.4 Infrared Absorption and Raman Scattering
- Example 8.6. Resonance Raman Spectrum of Red K2[Ni(dto)2] in Solid State
- 8.2.5 Transitions Involving Orbitally Degenerate States
- 8.3 X-ray and Ultraviolet Photoelectron Spectra
- EXAFS
- 8.3.1 General Ideas
- Example 8.7. Photoelectron Spectra of Specific Coordination Systems and Their Interpretation
- 8.3.2 Electron Relaxation
- Shakeup and CI Satellites
- Example 8.8. Configuration Interaction Satellite to the K+ 3s Emission Line in the UPS Spectrum of KF
- 8.3.3 Chemical Shift
- Example 8.9. The 1s Line of Nitrogen in the XPS of Different Coordination Systems Reflecting the Variety of Its Bonding in Different Groups
- 8.3.4 EXAFS and Related Methods
- Example 8.10. Applications of EXAFS Spectroscopy to a Variety of Problems
- 8.4 Magnetic Properrties
- 8.4.1 Magnetic Moment and Quenching of Orbital Contribution
- 8.4.2 Paramagnetic Susceptibility
- 8.4.3 Electron Spin Resonance (ESR)
- 8.4.4 Magnetic Exchange Coupling
- Example 8.11. Magnetic Exchange Coupling in Binuclear Copper Acetate Hydrate
- Example 8.12. The Nature of Metal-Metal Bonding in Binuclear Copper Acetate Hydrate
- 8.4.5 Spin Crossover
- 8.4.6 Magnetic Circular Dichroism (MCD)
- 8.5 Gamma-resonance Spectroscopy
- 8.5.1 The Mossbauer Effect
- 8.5.2 .-Resonance Spectra
- 8.5.3 Isomer Shift and Quadrupole Splitting in GRS
- 8.5.4 Hyperfine Splitting
- Example 8.13. Magnetic Hyperfine Structure in GRS of Coordination Compounds with a 57Fe Nucleus
- Example 8.14. Observation of Spin Crossover in the .-Resonance Spectrum of [Fe(phen)2 (NCS)2]
- 8.6 Electron Charge and Spin Density distribution in Diffraction Method
- 8.6.1 The Method of Deformation Density
- Example 8.15. Deformation Density in Sodium Nitroprusside (Direct Inspection)
- Example 8.16. Metal-Metal Bonding in Mn2(CO)10
- Fragment Deformation Density
- Example 8.17. Density Modeling for Fe(II)- Phthalocyanine and Co(II)-Tetraphenylporphyrin
- 8.6.2 Spin Densities from Neutron Scattering
- Example 8.18. Spin Distributions in Some Coordination Systems Obtained from Neutron Scattering
- Summary Notes
- Exercises and Problems
- References
- Chapter 9 Stereochemistry and Crystal Chemistry
- 9.1 Definitions. Semiclassical Approaches
- 9.1.1 The Notion of Molecular Shape
- 9.1.2 Directed Valences, Localized Electron Pairs, and Valence Shell Electron Pair Repulsion (VSEPR)
- 9.1.3 Nonbonding Orbitals and Nodal Properties
- Example 9.1. Influence of Nonbonding MOs on Coordination Geometry
- 9.1.4 Complementary Spherical Electron Density Model
- Example 9.2. The Inert-Gas Rule in Stereochemistry of Some Coordination Compounds
- 9.2 Vibronic Effects in Stereochemistry
- 9.2.1 Nuclear Motion Effects: Relativity to the Means of Observation and Vibronic Amplification of Distortions
- 9.2.2 Qualitative Stereochemical Effects of Jahn-Teller and Pseudo-Jahn-Teller Distortions
- Example 9.3. Stereochemistry of MXn Systems Controlled by Electronic Structure and Vibronic Coupling
- Example 9.4. Pseudo-JT Origin of Distortions in CuCl3- 5 Versus ZnCl3- 5
- 9.2.3 Off-Center Position of the Central Atom
- 9.2.4 Geometry of Ligand Coordination
- 9.2.5 Stereochemically Active and Inert Lone Pairs
- 9.2.6 Pseudorotations in Coordination Systems
- 9.3 Mutual Influence of Ligands
- 9.3.1 The Model: Trans and Cis Influences in Stereochemistry
- 9.3.2 Electronic Factors
- 9.3.3 Vibronic Theory of Ligand Mutual Influence
- 9.4 Crystal Stereochemistry
- 9.4.1 The Plasticity Effect
- 9.4.2 Distortion Isomers
- Example 9.5. Origin of Distortion Isomers in Cu (NH3)2 X2, X = Cl, Br
- 9.4.3 Temperature-Dependent Solid-State Conformers
- 9.4.4 Cooperative Effects: Order-Disorder and "Displacive" Phase Transitions and Helicoidal Structures
- Summary Notes
- Exercises and Problems
- References
- Chapter 10 Charge Transfer, Redox Properties, and Electron-conformational Effects
- 10.1 Electron Transfer and Charge Transfer by Coordination
- 10.1.1 Intramolecular Charge Transfer and Intermolecular Electron Transfer
- Example 10.1. Donor-acceptor PtII Complexes with Intramolecular Electron Transfer for Light Harvesting
- 10.1.2 Solvation-driven Charge Transfer
- 10.1.3 Redox Capacitance
- Example 10.2. Charge Transfer by Coordination of Peroxide to Iron Porphyrin
- 10.1.4 Hard and Soft Acids and Bases
- 10.2 Electron Transfer in Mixed-Valence Compounds
- 10.2.1 Mixed-Valence Compounds as Electronic Systems
- a Two-Level Dimer
- Example 10.3. The Creutz-Taube (CT) Ion as a Mixed-Valence System
- 10.2.2 Magnetic Properties
- 10.2.3 Mixed-Valence Trimers: Coexistence of Localized and Delocalized States
- Example 10.4. Tricenter Ferredoxin
- 10.3 Electron-Conformational Effects In Biological Systems
- 10.3.1 Distortions Produced by Excess Electronic Charge
- Special Features of Metalloenzymes
- 10.3.2 Trigger Mechanism of Hemoglobin Oxygenation: Comparison with Peroxidase
- Summary Notes
- Exercises and Problems
- References
- Chapter 11 Reactivity and Catalytic Action
- 11.1 Electronic Factors in Reactivity
- 11.1.1 Chemical Reactivity and Activated Complexes
- 11.1.2 Transition (Activation) States of Chemical Reactions Are Controlled by the Pseudo-Jahn-Teller Effect
- 11.1.3 Frontier Orbitals and Perturbation Theory
- 11.1.4 Orbital Symmetry Rules in Reaction Mechanisms
- Example 11.1. Orbital Symmetry Rules and Vibronic Coupling in Formation of Cyclobutane from Ethylene with Catalyst Participation
- 11.2 Electronic Control of Chemical Activation Via Vibronic Coupling
- 11.2.1 Chemical Activation by Electron Rearrangement
- 11.2.2 Activation of Small Molecules by Coordination
- Example 11.2. Activation of Carbon Monoxide
- Example 11.3. Numerical Estimate of CO Activation by Coordination to a NiO Surface
- Example 11.4. Numerical Estimates of N2, NO, and H2 Activation by Coordination to Transition Metal Centers
- Example 11.5. Activation of Oxygen by Hemoproteins
- Example 11.6. Quantum-mechanical Tunneling Reactions in Jahn-Teller Distorted Cu(II)N6 Complexes
- 11.3 Direct Computation of Energy Barriers of Chemical Reactions
- 11.3.1 Substitution Reactions: The trans Effect
- 11.3.2 Ligand Coupling and Cleavage Processes
- 11.3.3 Insertion Reactions
- 11.3.4 Photochemical Reactions of Organometallics
- Example 11.7. Photochemistry of Ru(bpy)3 2+
- Summary Notes
- Questions and Problems
- References
- Appendix 1. Tables of Characters of Irreducible Representations of Most Usable Symmetry Point Groups and Direct Products of Some Representations
- Appendix 2. General Expressions for the Matrix Element Vmm of Perturbation of the States of one d Electron in Crystal Fields of Arbitrary Symmetry
- Appendix 3. Calculation of the Destabilization and Splitting of the States of One d Electron in Crystal Fields of Different Symmetries
- Appendix 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
- Appendix 5. Matrix Elements of Crystal Field Perturbation of f-Electron States
- Answers and Solutions
- Subject Index
- EULA
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