A Chemist's Guide to Valence Bond Theory : Insights into Chemical Bonding, Reactivity, and Excited States

• Autore: Shaik Sason
• Pubblicazione: Newark : , : John Wiley & Sons, Incorporated, , 2025; ©2026
• Edizione: 2nd ed.
• Descrizione fisica: 1 online resource (481 pages)
• Nota di contenuto: Cover -- 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. ; 3.5.4 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. ; References -- 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. ; 6.9 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. ; 9.2.5 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. ; 11.2.2 Multiple Two‐Electron Bonds.
• Sommario/riassunto: 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.
• Titolo autorizzato: Chemist's guide to valence bond theory
• ISBN: 1-394-23882-7; 1-394-23880-0
• Formato: Materiale a stampa
• Livello bibliografico: Monografia
• Lingua di pubblicazione: Inglese
• Record Nr.: 9911054511503321
• Lo trovi qui: Univ. Federico II