LEADER 10823nam 22004453 450 001 9911054511503321 005 20251227060318.0 010 $a1-394-23882-7 010 $a1-394-23880-0 035 $a(MiAaPQ)EBC32467201 035 $a(Au-PeEL)EBL32467201 035 $a(CKB)44564471000041 035 $a(EXLCZ)9944564471000041 100 $a20251227d2025 uy 0 101 0 $aeng 135 $aurcnu|||||||| 181 $ctxt$2rdacontent 182 $cc$2rdamedia 183 $acr$2rdacarrier 200 12$aA Chemist's Guide to Valence Bond Theory $eInsights into Chemical Bonding, Reactivity, and Excited States 205 $a2nd ed. 210 1$aNewark :$cJohn Wiley & Sons, Incorporated,$d2025. 210 4$dİ2026. 215 $a1 online resource (481 pages) 311 08$a1-394-23879-7 327 $aCover -- Title Page -- Copyright -- Contents -- Chapter 1 A Brief Story of Valence Bond Theory, its Rivalry with Molecular Orbital Theory, its Demise, and Resurgence -- 1.1 Roots of VB Theory -- 1.2 Origins of MO Theory and the Roots of VB-MO Rivalry -- 1.3 One Theory is Up, The Other is Down -- 1.4 Mythical Failures of VB Theory: More Ground is Gained by MO Theory -- 1.5 Are the Failures of VB Theory Real? -- 1.5.1 The O2 Failure -- 1.5.2 The C4H4 Failure -- 1.5.3 The C5H5+ Failure -- 1.5.4 The Failure Associated with the Photoelectron Spectroscopy of CH4 -- 1.6 Valence Bond is a Legitimate Theory Alongside Molecular Orbital Theory -- 1.7 Modern VB Theory: Valence Bond Theory is Coming of Age -- References -- Chapter 2 A Brief Tour Through Some Valence Bond Outputs and Terminology -- 2.1 Valence Bond Output for the H2 Molecule -- 2.2 Valence Bond Mixing Diagrams -- 2.3 Valence Bond Output for the HF Molecule -- References -- Chapter 3 Basic Valence Bond Theory -- 3.1 Writing and Representing Valence Bond Wave Functions -- 3.1.1 VB Wave Functions with Localized Atomic Orbitals -- 3.1.2 Valence Bond Wave Functions with Semilocalized AOs -- 3.1.3 Valence Bond Wave Functions with Fragment Orbitals -- 3.1.4 Writing Valence Bond Wave Functions Beyond the 2e/2c Case -- 3.1.5 Pictorial Representation of Valence Bond Wave Functions by Bond Diagrams -- 3.2 Overlaps Between Determinants -- 3.3 Valence Bond Formalism Using the Exact Hamiltonian -- 3.3.1 Purely Covalent Singlet State and a Triplet Repulsive State -- 3.3.2 Configuration Interaction Involving Ionic Terms -- 3.4 Valence Bond Formalism Using an Effective Hamiltonian -- 3.5 Some Simple Formulas for Elementary Interactions -- 3.5.1 The Two?Electron Bond -- 3.5.2 Repulsive Interactions in Valence Bond Theory -- 3.5.3 Mixing of Degenerate Valence Bond Structures. 327 $a3.5.4 Nonbonding Interactions in Valence Bond Theory -- 3.6 Structural Coefficients and Weights of Valence Bond Wave Functions -- 3.7 Bridges Between Molecular Orbital and Valence Bond Theories -- 3.7.1 Comparison of Qualitative Valence Bond and Molecular Orbital Theories -- 3.7.2 The Relationship Between Molecular Orbital and Valence Bond Wave Functions -- 3.7.3 Localized Bond Orbitals: A Pictorial Bridge Between Molecular Orbital and Valence Bond Wave Functions -- 3.A.1 Normalization Constants, Energies, Overlaps, and Matrix Elements of Valence Bond Wave Functions -- 3.A.1.1 Energy and Self?Overlap of an Atomic Orbital?Based Determinants -- 3.A.1.2 Hamiltonian Matrix Elements and Overlaps Between Atomic Orbital?Based Determinants -- 3.A.2 GUIDELINES FOR VALENCE BOND MIXING -- REFERENCES -- EXERCISES -- Answers -- Chapter 4 Mapping Molecular Orbital-Configuration Interaction to Valence Bond Wave Functions -- 4.1 Generating a Set of Valence Bond Structures -- 4.2 Mapping a Molecular Orbital-Configuration Interaction Wave Function into a Valence Bond Wave Function -- 4.2.1 Expansion of Molecular Orbital Determinants in Terms of Atomic Orbital Determinants -- 4.2.2 Projecting the Molecular Orbital-Configuration Interaction Wave Function to the Rumer Basis of Valence Bond Structures -- 4.2.3 An Example: The Hartree-Fock Wave Function of Butadiene -- 4.3 Using Half?Determinants to Calculate Overlaps between Valence Bond Structures -- References -- EXERCISES -- Answers -- Chapter 5 Are The "Failures" of Valence Bond Theory Real? -- 5.1 Introduction -- 5.2 The Triplet Ground State of Dioxygen -- 5.3 Aromaticity-Antiaromaticity in Ionic Rings CnHn& -- pm -- -- 5.4 Aromaticity/Antiaromaticity in Neutral Rings -- 5.5 The Valence Ionization Spectrum of CH4 -- 5.6 The Valence Ionization Spectrum of H2O and the "Rabbit?Ear" Lone Pairs -- 5.7 A Summary. 327 $aReferences -- Exercises -- Answers -- Chapter 6 Valence Bond Diagrams for Chemical Reactivity -- 6.1 Introduction -- 6.2 Two Archetypal Valence Bond Diagrams -- 6.3 The Valence Bond State Correlation Diagram Model and its General Outlook on Reactivity -- 6.4 Construction of Valence Bond State Correlation Diagrams for Elementary Processes -- 6.4.1 Valence Bond State Correlation Diagrams for Radical Exchange Reactions -- 6.4.2 Valence Bond State Correlation Diagrams for Reactions Between Nucleophiles and Electrophiles -- 6.4.3 Generalization of Valence Bond State Correlation Diagrams for Reactions Involving Reorganization of Covalent Bonds -- 6.5 Barrier Expressions Based on the Valence Bond State Correlation Diagram Model -- 6.5.1 Some Guidelines for Quantitative Applications of the Valence Bond State Correlation Diagram Model -- 6.6 Making Qualitative Reactivity Predictions with the Valence Bond State Correlation Diagram -- 6.6.1 Reactivity Trends in Radical Exchange Reactions -- 6.6.2 Reactivity Trends in Allowed and Forbidden Reactions -- 6.6.3 Reactivity Trends in Oxidative-Addition Reactions -- 6.6.4 Reactivity Trends in Reactions Between Nucleophiles and Electrophiles -- 6.6.5 Chemical Significance of the f Factor -- 6.6.6 Making Stereochemical Predictions with the VBSCD Model -- 6.6.7 Predicting Transition?State Structures with the Valence Bond State Correlation Diagram Model -- 6.6.8 Trends in Transition?State Resonance Energies -- 6.7 Valence Bond Configuration Mixing Diagrams: General Features -- 6.8 Valence Bond Configuration Mixing Diagram with Ionic Intermediate Curves -- 6.8.1 Valence Bond Configuration Mixing Diagram for Proton?Transfer Processes -- 6.8.2 Insights from Valence Bond Configuration Mixing Diagrams: One Electron Less-One Electron More -- 6.8.3 Nucleophilic Substitution on Silicon: Stable Hypercoordinated Species. 327 $a6.9 Valence Bond Configuration Mixing Diagram with Intermediates Nascent From "Foreign States" -- 6.9.1 The Mechanism of Nucleophilic Substitution of Esters -- 6.9.2 The SRN2 and SRN2c Mechanisms -- 6.10 Valence Bond State Correlation Diagram: A General Model for Electronic Delocalization in Clusters -- 6.10.1 What is the Driving Force for the D6h Geometry of Benzene, & -- bfsigma -- or & -- bfpi -- ? -- 6.11 Valence Bond State Correlation Diagram: Application to Photochemical Reactivity -- 6.11.1 Photoreactivity in 3e/3c Reactions -- 6.11.2 Photoreactivity in 4e/3c Reactions -- 6.12 A Summary -- References -- OUTPUT 6.13 -- EXERCISES -- Answers -- Chapter 7 Using Valence Bond Theory to Compute and Conceptualize Excited States -- 7.1 Excited States of a Single Bond -- 7.2 Excited States of Molecules with Conjugated Bonds -- 7.2.1 Use of Molecular Symmetry to Generate Covalent Excited States Based on Valence Bond Theory -- 7.2.2 Covalent Excited States of Polyenes -- 7.3 A Summary -- References -- Exercises -- Answers -- Chapter 8 Spin Hamiltonian Valence Bond Theory and its Applications to Organic Radicals, Diradicals, and Polyradicals -- 8.1 A Topological Semiempirical Hamiltonian -- 8.2 Applications -- 8.2.1 Ground States of Polyenes and Hund's Rule Violations -- 8.2.2 Spin Distribution in Alternant Radicals -- 8.2.3 Relative Stabilities of Polyenes -- 8.2.4 Extending Ovchinnikov's Rule to Search for Bistable Hydrocarbons -- 8.3 A Summary -- References -- Exercises -- Answers -- Chapter 9 Currently Available Ab Initio Valence Bond Computational Methods and Their Principles -- 9.1 Introduction -- 9.2 Valence Bond Methods Based on Semi?Localized Orbitals -- 9.2.1 The Generalized Valence Bond Method -- 9.2.2 The Spin?Coupled Generalized Valence Bond Method -- 9.2.3 The CASVB Method -- 9.2.4 The Generalized Resonating Valence Bond Method. 327 $a9.2.5 Multiconfiguration Valence Bond Methods with Optimized Orbitals -- 9.3 Valence Bond Methods Based on Localized Orbitals -- 9.3.1 Valence Bond Self?Consistent Field Method with Localized Orbitals -- 9.3.2 The Breathing?Orbital Valence Bond Method -- 9.3.3 The Valence Bond Configuration Interaction Method -- 9.3.4 The Valence Bond Quantum Monte Carlo Method -- 9.4 Methods for Getting Valence Bond Quantities from Molecular Orbital?Based Procedures -- 9.4.1 Using Standard Molecular Orbital Software to Compute Single Valence Bond Structures or Determinants -- 9.4.2 The Block?Localized Wave Function and Related Methods -- 9.5 A Valence Bond Method with Polarizable Continuum Model -- 9.6 Perspective -- 9.A.1 Some Available Valence Bond Programs -- 9.A.1.1 The TURTLE Software -- 9.A.1.2 The XMVB Program -- 9.A.1.3 The CRUNCH Software -- 9.A.1.4 The VB2000 Software -- 9.A.1.5 The CHAMP Program for the VB?QMC Method -- 9.A.2 Implementations of Valence Bond Methods in Standard Ab Initio Packages -- References -- Gaussian Input 9.1 -- Gaussian Input 9.2 -- Chapter 10 Do Your Own Valence Bond Calculation-A Practical Guide -- 10.1 Introduction -- 10.2 Wave Functions and Energies for the Ground State of F2 -- 10.2.1 GVB, SC, and VBSCF Methods -- 10.2.2 The BOVB Method -- 10.2.3 The VBCI Method -- 10.3 Valence Bond Calculations of Diabatic States and Resonance Energies -- 10.3.1 Definition of Diabatic States -- 10.3.2 Calculations of Meaningful Diabatic States -- 10.3.3 Resonance Energies -- 10.4 Comments on Calculations of VBSCDS and VBCMDS -- 10.4.1 VBSCD Calculations -- 10.4.2 VBCMD Calculations -- 10.A.1 Calculating at the SD?BOVB Level in Low Symmetry Cases -- References -- Chapter 11 The Chemical Bonds in Valence Bond Theory -- 11.1 Introduction -- 11.2 VB Approaches: Their Bond Descriptions and Representations -- 11.2.1 Single Two?Electron Bonds. 327 $a11.2.2 Multiple Two?Electron Bonds. 330 $aUpdated 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. 700 $aShaik$b Sason$0600771 801 0$bMiAaPQ 801 1$bMiAaPQ 801 2$bMiAaPQ 906 $aBOOK 912 $a9911054511503321 996 $aChemist's guide to valence bond theory$91023580 997 $aUNINA