A Chemist's Guide to Valence Bond Theory
Since the 1980s, valence bond (VB) theory has enjoyed a renaissance characterized both in the qualitative application of the theory and in the development of new methods for its computer implementation. Written by leading authorities, this is the premier reference on current VB theory and applications in a pedagogical context, perhaps the first such attempt since Pauling's The Nature of the Chemical Bond. After an introduction, A Chemist's Guide to Valence Bond Theory pre-sents a practical system that can be applied to a variety of chemical problems in a uniform manner. Concise yet comprehensive, it includes:
A tour of some VB outputs and terminology
An explanation of basic VB theory
A discussion of various applications of the VB method to chemical problems, encompassing bonding problems, aromaticity and antiaromaticity, the dioxygen molecule, polyradicals, excited states, organic reactions, inorganic/organometallic reactions, photochemical reactions, and catalytic reactions
Samples of inputs/outputs and instructions for interpreting results
A short programmable outline for converting molecular orbital wave functions to VB structures
A guide for performing VB calculations
Complete with exercises and answers at the end of chapters, numerous solved problems, and a glossary of terms and symbols, this is the authoritative guide for computational chemists, chemical physicists, and research chemists in organic and organometallic/inorganic chemistry concerned with reactivity and molecular structure. It is also an excellent text for advanced undergraduate and graduate students.
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?
1.6. VB is a Legitimate Theory Alongside Molecular Orbital Theory.
1.7. Modern VB Theory: Valence Bond Theory is Coming of Age.
Chapter 2. A Brief Tour Through Some Valence Bond Outputs and Terminology.
2.1. Valence Bond Output for the H<sup>2</sup> Molecule.
2.2. Valence Bond Mixing Diagrams.
2.3. Valence Bond Output for the HF Molecule.
Chapter 3. Basic Valence Bond Theory.
3.1. Writing and Representing Valence Bond Wave.
3.2 Overlaps between Determinants.
3.3 Valence Bond Formalism Using the Exact Hamiltonian.
3.4 Valence Bond Formalism using an Effective Hamiltonian.
3.5 Some Simple Formulas for Elementary Interactions.
3.6 Structural Coefficients and Weights of Valence Bond Wave Function.
3.7 Bridges Between Molecular Orbital and Valence Bond Theories.
Chapter 4. Mapping Molecular Orbitals-Configuration Interaction to Valence Bond Wave Functions.
4.1. Generating a Set of Valence Bond structures.
4.2. Mapping a Molecular Orbital-Configuration Interaction.
4.3. Using Half-Determinants to Calculate Overlaps between Valence Bond Structures.
5. Are the "Failures" of Valence Bond Theory Real?
5.2. The Triplet Ground State of Dioxygen.
5.3. Aromaticity-Antiaromaticity in Ionic Rings CnHn+/-
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.
6. Valence Bond Diagrams for Chemical Reactivity.
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 Valance Bond State Correlation Diagram Model and Its General Outlook on Reactivity.
6.4. Construction of Valence Bond State Correlation Diagrams for Elementary Processes.
6.5. Barrier Expressions Based on the Valence Bond State Correlation Diagram Model.
6.6. Making Qualitative Reactivity Predictions with the Valence Bond State Correlation Diagram.
6.7. Valence Bond Configuration Mixing Diagrams: General Features.
6.8. Valence Bond Configuration Mixing Diagram with Ionic Intermediate Curves.
6.9. Valence Bond Configuration Mixing Diagram with Intermediates Nascent from "Foreign States".
6.10. Valence Bond State Correlation Diagram: A General Model for Electronic Delocalization in Clusters.
6.11. Valence Bond State Correlation Diagram: Application to Photochemical Reactivity.
6.12. A Summary.
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.
7.3. A Summary.
8. Spin Hamiltonian Valence bond Theory and its Applications to Organic Radicals, Diradicals, and Polyradicals.
8.1. A Topological Semiempirical Hamiltonian.
8.3. A Summary.
9. Currently Available AB Initio Valence Bond Computational Methods and their Principles.
9.2. Valence Bond Methods Based on Semilocalized Orbitals.
9.3. Valence Bond Methods Based on Localized Orbitals.
9.4. Methods for Getting Valence Bond Quantities.
9.5. A Valence Bond Methods with Polarizable Continuum Model.
10. Do Your Own Valence Bond Calculations-A Practical Guide.
10.2. Wave Functions and Energies for the Ground State of F2.
10.3. Valence Bond Calculations of Diabatic States and Resonance Energies.
10.4. Comments on Calculations of VBSCDs and VBCMDs.
Philippe C. Hiberty is Director of Research at the Centre National de la Recherche Scientifique (CNRS) and a member of the Theoretical Chemistry Group in the Laboratoire de Chimie Physique at the?University of Paris-Sud. He taught quantum chemistry for years at the Ecole Polytechique in Palaiseau. He received the Grand Prix Philippe A. Guye from the French Academy of Sciences in 2002. Under the supervision of Professor Lionel Salem, he devoted his PhD to building a bridge between MO and VB theories by devising a method for mapping MO wave functions to VB ones. In collaboration with Professor Sason Shaik, he applied VB theory to fundamental concepts of organic chemistry such as aromaticity, hypervalence, odd-electron bonds, prediction of reaction barriers from properties of reactants and products, and so on. He is the originator of the Breathing-Orbital Valence Bond method, which is aimed at combining the lucidity of compact VB wave functions with a good accuracy of the energetics.
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