Overview

Updated resource on theoretical aspects and applications of valence bond methods to chemical calculations A Chemist’s Guide to Valence Bond Theory explains how to use valence bond theory to think concisely and rigorously and how to use VB computations. It familiarizes the reader with the various VB-based computational tools and methods available today and their use for a given chemical problem and provides samples of inputs/outputs that instruct the reader on how to interpret the results. The book also covers the theoretical basis of Valence Bond (VB) theory and its applications to chemistry in the ground- and excited-states. Applications discussed in the book include sets of exercises and corresponding answers on bonding problems, organic reactions, inorganic/organometallic reactions, and bioinorganic/ biochemical reactions. This Second Edition contains a new chapter on chemical bonds which includes sections on covalent, ionic, and charge-shift bonds as well as triplet bond pairs, a new chapter on the Breathing-Orbital VB method with its application to molecular excited states, and several new sections discussing recent developments such as DFT-based methods and solvent effects via the Polarizable Continuum Model (PCM). A Chemist’s Guide to Valence Bond Theory includes information on: Writing and representing valence bond wave functions, overlaps between determinants, and valence bond formalism using the exact Hamiltonian Generating a set of valence bond structures and mapping a molecular orbital-configuration interaction wave function into a valence bond wave function The alleged “failures” of valence bond theory, such as the triplet ground state of dioxygen, and whether or not these failures are “real” Spin Hamiltonian valence bond theory and its applications to organic radicals, diradicals, and polyradicals A Chemist’s Guide to Valence Bond Theory is an essential reference on the subject for chemists who are not necessarily experts on theory but have some background in quantum chemistry. The text is also appropriate for upper undergraduate and graduate students in advanced courses on valence bond theory.

Full Product Details

Author:   Sason Shaik (Hebrew University of Jerusalem, Jerusalem, Israel) ,  David Danovich (Hebrew University of Jerusalem, Jerusalem, Israel) ,  Philippe C. Hiberty (Université de Paris-Sud, France)
Publisher:   John Wiley & Sons Inc
Imprint:   John Wiley & Sons Inc
Edition:   2nd edition
ISBN:  

9781394238798

ISBN 10:   1394238797
Pages:   480
Publication Date:   06 January 2026
Audience:   Professional and scholarly ,  Professional & Vocational
Format:   Hardback
Publisher's Status:   Active
Availability:   Out of stock  
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Table of Contents

PREFACE   1 A Brief Story of Valence Bond Theory, Its Rivalry with    Molecular Orbital Theory, Its Demise, and Resurgence 1   1.1 Roots of VB Theory 2   1.2 Origins of MO Theory and the Roots of VB–MO Rivalry 5   1.3 One Theory is Up the Other is Down 7   1.4 Mythical Failures of VB Theory: More Ground is    Gained by MO Theory 8   1.5 Are the Failures of VB Theory Real? 12   1.5.1 The O2 Failure 12   1.5.2 The C4H4 Failure 13   1.5.3 The C5H5+ Failure 13   1.5.4 The Failure Associated with the Photoelectron Spectroscopy of CH4 13   1.6 Valence Bond is a Legitimate Theory Alongside    Molecular Orbital Theory 14   1.7 Modern VB Theory: Valence Bond Theory is Coming    of Age 14   2 A Brief Tour Through Some Valence Bond Outputs    and Terminology 26   2.1 Valence Bond Output for the H2 Molecule 26   2.2 Valence Bond Mixing Diagrams 32   2.3 Valence Bond Output for the HF Molecule 33   3 Basic Valence Bond Theory 40   3.1 Writing and Representing Valence Bond Wave Functions 40   3.1.1 VB Wave Functions with Localized Atomic    Orbitals 40   3.1.2 Valence Bond Wave Functions with    Semilocalized AOs 41   3.1.3 Valence Bond Wave Functions with    Fragment Orbitals 42   3.1.4 Writing Valence Bond Wave Functions    Beyond the 2e/2c Case 43   3.1.5 Pictorial Representation of Valence Bond    Wave Functions by Bond Diagrams 45   3.2 Overlaps between Determinants 45   3.3 Valence Bond Formalism Using the Exact Hamiltonian 46   3.3.1 Purely Covalent Singlet and Triplet    Repulsive States 47   3.3.2 Configuration Interaction Involving Ionic    Terms 49   3.4 Valence Bond Formalism Using an Effective    Hamiltonian 49   3.5 Some Simple Formulas for Elementary Interactions 51   3.5.1 The Two-Electron Bond 51   3.5.2 Repulsive Interactions in Valence Bond    Theory 52   3.5.3 Mixing of Degenerate Valence Bond    Structures 53   3.5.4 Nonbonding Interactions in Valence Bond    Theory 54   3.6 Structural Coefficients and Weights of Valence Bond    Wave Functions 56   3.7 Bridges between Molecular Orbital and Valence Bond    Theories 56   3.7.1 Comparison of Qualitative Valence Bond    and Molecular Orbital Theories 57   3.7.2 The Relationship between Molecular Orbital    and Valence Bond Wave Functions 58   3.7.3 Localized Bond Orbitals: A Pictorial Bridge    between Molecular Orbital and Valence Bond    Wave Functions 60    Appendix 65    3.A.1 Normalization Constants, Energies, Overlaps, and    Matrix Elements of Valence Bond Wave Functions 65    3.A.1.1 Energy and Self-Overlap of an Atomic    Orbital- Based Determinant 66    3.A.1.2 Hamiltonian Matrix Elements and Overlaps    between Atomic Orbital-Based Determinants 68    3.A.2 Simple Guidelines for Valence Bond Mixing 68   Exercises 70   Answers 74   4 Mapping Molecular Orbital—Configuration    Interaction to Valence Bond Wave Functions 81   4.1 Generating a Set of Valence Bond Structures 81   4.2 Mapping a Molecular Orbital–Configuration Interaction    Wave Function into a Valence Bond Wave Function 83   4.2.1 Expansion of Molecular Orbital Determinants    in Terms of Atomic Orbital Determinants 83   4.2.2 Projecting the Molecular Orbital–Configuration    Interaction Wave Function onto the Rumer    Basis of Valence Bond Structures 85   4.2.3 An Example: The Hartree–Fock Wave    Function of Butadiene 86   4.3 Using Half-Determinants to Calculate Overlaps    between Valence Bond Structures 88    Exercises 89    Answers 90   5 Are the ‘‘Failures’’ of Valence Bond Theory Real? 94   5.1 Introduction 94   5.2 The Triplet Ground State of Dioxygen 94   5.3 Aromaticity–Antiaromaticity in Ionic Rings CnHn+/- 97   5.4 Aromaticity/Antiaromaticity in Neutral Rings 100   5.5 The Valence Ionization Spectrum of CH4 104   5.6 The Valence Ionization Spectrum of H2O and the    ‘‘Rabbit-Ear’’ Lone Pairs 106   5.7 A Summary 109    Exercises 111    Answers 112   6 Valence Bond Diagrams for Chemical Reactivity 116   6.1 Introduction 116   6.2 Two Archetypal Valence Bond Diagrams 116   6.3 The Valence Bond State Correlation Diagram Model    and Its General Outlook on Reactivity 117   6.4 Construction of Valence Bond State Correlation    Diagrams for Elementary Processes 119   6.4.1 Valence Bond State Correlation Diagrams    for Radical Exchange Reactions 119   6.4.2 Valence Bond State Correlation Diagrams    for Reactions between Nucleophiles and    Electrophiles 122   6.4.3 Generalization of Valence Bond State    Correlation Diagrams for Reactions    Involving Reorganization of Covalent Bonds 124   6.5 Barrier Expressions Based on the Valence Bond State    Correlation Diagram Model 126   6.5.1 Some Guidelines for Quantitative Applications    of the Valence Bond State Correlation Diagram    Model 128   6.6 Making Qualitative Reactivity Predictions with the    Valence Bond State Correlation Diagram 128   6.6.1 Reactivity Trends in Radical Exchange    Reactions 130   6.6.2 Reactivity Trends in Allowed and Forbidden    Reactions 132   6.6.3 Reactivity Trends in Oxidative–Addition    Reactions 133   6.6.4 Reactivity Trends in Reactions between    Nucleophiles and Electrophiles 136   6.6.5 Chemical Significance of the f Factor 138   6.6.6 Making Stereochemical Predictions with the    VBSCD Model 138   6.6.7 Predicting Transition State Structures with    the Valence Bond State Correlation Diagram    Model 140   6.6.8 Trends in Transition State Resonance Energies 141   6.7 Valence Bond Configuration Mixing Diagrams: General    Features 144   6.8 Valence Bond Configuration Mixing Diagram with Ionic    Intermediate Curves 144   6.8.1 Valence Bond Configuration Mixing Diagrams    for Proton-Transfer Processes 145   6.8.2 Insights from Valence Bond Configuration    Mixing Diagrams: One Electron Less–One    Electron More 146   6.8.3 Nucleophilic Substitution on Silicon: Stable    Hypercoordinated Species 147   6.9 Valence Bond Configuration Mixing Diagram with    Intermediates Nascent from ‘‘Foreign States’’ 149   6.9.1 The Mechanism of Nucleophilic Substitution    of Esters 149   6.9.2 The SRN2 and SRN2c Mechanisms 150   6.10 Valence Bond State Correlation Diagram: A General    Model for Electronic Delocalization in Clusters 153    6.10.1 What is the Driving Force for the D6h    Geometry of Benzene, s or p? 154   6.11 Valence Bond State Correlation Diagram: Application    to Photochemical Reactivity 157   6.11.1 Photoreactivity in 3e/3c Reactions 158   6.11.2 Photoreactivity in 4e/3c Reactions 159   6.12 A Summary 163    Exercises 171    Answers 176   7 Using Valence Bond Theory to Compute and    Conceptualize Excited States 193   7.1 Excited States of a Single Bond 194   7.2 Excited States of Molecules with Conjugated Bonds 196   7.2.1 Use of Molecular Symmetry to Generate    Covalent Excited States Based on Valence    Bond Theory 197   7.2.2 Covalent Excited States of Polyenes 209   7.3 A Summary 212    Exercises 215    Answers 216   8 Spin Hamiltonian Valence Bond Theory and its    Applications to Organic Radicals, Diradicals, and    Polyradicals 222   8.1 A Topological Semiempirical Hamiltonian 223   8.2 Applications 225   8.2.1 Ground States of Polyenes and Hund’s Rule    Violations 225   8.2.2 Spin Distribution in Alternant Radicals 227   8.2.3 Relative Stabilities of Polyenes 228   8.2.4 Extending Ovchinnikov’s Rule to Search for    Bistable Hydrocarbons 230   8.3 A Summary 231    Exercises 232    Answers 234   9 Currently Available Ab Initio Valence Bond    Computational Methods and their Principles 238   9.1 Introduction 238   9.2 Valence Bond Methods Based on Semilocalized Orbitals 239   9.2.1 The Generalized Valence Bond Method 240   9.2.2 The Spin-Coupled Valence Bond Method 242   9.2.3 The CASVB Method 243   9.2.4 The Generalized Resonating Valence Bond    Method 245   9.2.5 Multiconfiguration Valence Bond Methods    with Optimized Orbitals 246   9.3 Valence Bond Methods Based on Localized Orbitals 247   9.3.1 Valence Bond Self-Consistent Field Method    with Localized Orbitals 247   9.3.2 The Breathing-Orbital Valence Bond Method 249   9.3.3 The Valence Bond Configuration Interaction    Method 252   9.4 Methods for Getting Valence Bond Quantities from    Molecular Orbital-Based Procedures 253   9.4.1 Using Standard Molecular Orbital Software    to Compute Single Valence Bond Structures    or Determinants 253   9.4.2 The Block-Localized Wave Function and    Related Methods 254   9.5 A Valence Bond Method with Polarizable Continuum    Model 255    Appendix 257    9.A.1 Some Available Valence Bond Programs 257    9.A.1.1 The TURTLE Software 257    9.A.1.2 The XMVB Program 257    9.A.1.3 The CRUNCH Software 257    9.A.1.4 The VB2000 Software 258    9.A.2 Implementations of Valence Bond Methods in    Standard Ab Initio Packages 258   10 Do Your Own Valence Bond Calculations—A    Practical Guide 271   10.1 Introduction 271   10.2 Wave Functions and Energies for the Ground State    of F2 271   10.2.1 GVB, SC, and VBSCF Methods 272   10.2.2 The BOVB Method 276   10.2.3 The VBCI Method 280   10.3 Valence Bond Calculations of Diabatic States and    Resonance Energies 281   10.3.1 Definition of Diabatic States 282   10.3.2 Calculations of Meaningful Diabatic States 282   10.3.3 Resonance Energies 284   10.4 Comments on Calculations of VBSCDs and VBCMDs 287   Appendix 290   10.A.1 Calculating at the SD–BOVB Level in Low    Symmetry Cases 290   11 The Chemical Bonds in Valence Bond Theory 304   11.1 Introduction 304   11.2 VB Approaches: Their Bond Descriptions and Representations 304   11.2.1 Single Two-Electron Bonds 304   11.2.2 Multiple Two-Electron Bonds 306   11.2.3 Classical VB Methods for Single Bonds 306   11.2.4 VB Methods for Multiple Bonds 307   11.3 Applications of VB Theory to Chemical Bonding 309   11.3.1 Electron-Pair Bonds 309    11.3.1.1 The Logic Behind the Existence of    Three Bond Families 314    11.3.1.2 Do Other Computational Methods    Reveal the CSB Family? 315   11.3.2 Pauli Repulsion: The Major Driver of CSB 317    11.3.2.1 Bonds Between Main Elements 318    11.3.2.2 Bonds Between Transition Metals    (TMs) 320    11.3.2.3 Post Transition Metals, Groups 11    and 12 321    11.3.2.4 Other CSB Factors 321       11.3.3 Experimental Manifestations of CSB 322   11.3.4 Deducing Bonding Features from Energy    Barriers 323   11.3.5 Unique Features of Charge-Shift Bonds 324   11.4 Why and When will Atoms Form Hypervalent    Molecules? 325   11.5 Features of Orbital Hybridization in Modern VB    Theory 328   11.5.1 Overlaps of Optimized Hybrid Orbitals 329   11.5.2 Typical Molecules and Their Variationally    Optimized Hybrid Orbitals 330    11.5.2.1 Tetrahedral Hybrids in CH4, B and    N 330    11.5.2.2 Tetrahedral Hybrids 332    11.5.2.3 Linear Hybrids 333   11.5.3 An Overview of Hybridization Results 333    11.5.3.1 Summary of Hybridization Trends in    Classical VB Theory 334    11.6 Description of Multipole Bonding 334    11.6.1 The Bond Multiplicity of C2 335    11.6.2 Multi-Structure VBSCF Calculations of C2 335    11.6.2.1 The Covalent VB-Structure Set 336    11.6.2.2 Adding the Ionic Structures 337   11.6.3 Properties of Quadruply-Bonded Species 342    11.6.3.1 The Resonance-Energy Effect of    Doubly-Bonded Structures on    Quadruple Bonds 343    11.6.3.2 The Nature of the s-Bonds in C2 343    11.6.3.3 The Exo s-Bonds in C2 344   11.6.4 Some Lessons from the C2 Study 344   11.6.5 The Kinetic Stability of Dioxygen    Originates in the Cooperative p-Three-    Electron Bonding 345   11.6.6 Outcomes of p-s Interplay in Multiple    Bonding 347    11.6.6.1 The p-s Interplay in Benzene: What    Factor Determines the D6h Structure? 348    11.6.6.2 The p-s Interplay in Triply-Bonded    Molecules 352    11.6.6.2.1 Conclusions and Extensions of    the p-s Interplay 353        11.7 Triplet-Pair Bonds (TPB) in Ferromagnetic    Metal-Clusters 354   11.7.1 VB Modelling of Bonding in Triplet-Pair    Bonds 357   11.7.2 VB Modelling of n+1Mn Clusters 360   11.7.3 Bond Energies of Triplet-Pair Bonds 364   11.7.4 A Summary of No-Pair Bonding 365    11.8 Concluding Remarks 368    11.9 Supporting Information 368    11.9.1 Supplementary Issues 368    11.9.2 VB Structures for C2 370    11.9.3 Pauli Repulsion and VB Structure Counts    For Triplet-Pair Bond (TPB) in No-Pair    Clusters 377    11.9.3.1 Coinage Metal Clusters 377    11.9.3.2 Alkali Metal Clusters 379   12 Breathing-Orbital Valence Bond: Methods and    Applications 391   12.1 Introduction 391   12.2 Methodology 391    12.2.1 From VBSCF to BOVB 392    12.2.2 Static and Dynamic Correlations in    Electron-Pair Bonds 393    12.2.3 Odd-Electron Bonds 395    12.2.4 Spin-Unrestricted VBSCF and BOVB    Methods 398   12.3 Some Applications of the BOVB Method 398    12.3.1 A Quantitative Definition of Diradical    Character 398    12.3.2 When the Diradical Character Rules the    Reaction Barriers 400    12.3.3 Fast, Accurate and Insightful Calculations    of Challenging Excited States 403    12.3.3.1 The V State of Ethylene 403    12.3.3.2 The Low-Lying Excited States of Ozone    and Sulfur Dioxide 406   12.4 Concluding Remarks 410    12.4.1 The Specific Insight Provided by VB    Ab Initio Computations 410    12.4.2 Non-Orthogonality: A Handicap or an    Opportunity? 411   Epilogue 416   Glossary 418   Index 423

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Sason Shaik is a Saerree K. and Louis P. Fiedler Emeritus Professor of Chemistry at the Hebrew University. He has developed a number of new paradigms and concepts using valence bond theory and participated in the initiation of various valence bond methods. David Danovich is a senior computational chemist at the Institute of Chemistry in the Hebrew University, and an expert on VB calculations Philippe C. Hiberty is an Emeritus Director of Research at the Centre National de la Recherche Scientifique in the Université Paris-Saclay. He has developed the Breathing-Orbital VB method.

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