A Chemist's Guide to Valence Bond Theory

A Chemist's Guide to Valence Bond Theory

By: Philippe C. Hiberty (author), Sason S. Shaik (author)Hardback

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This reference on current VB theory and applications presents a practical system that can be applied to a variety of chemical problems in a uniform manner. After explaining basic VB theory, it discusses VB applications to bonding problems, aromaticity and antiaromaticity, the dioxygen molecule, polyradicals, excited states, organic reactions, inorganic/organometallic reactions, photochemical reactions, and catalytic reactions. With a guide for performing VB calculations, exercises and answers, and numerous solved problems, this is the premier reference for practitioners and upper-level students.

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About Author

Sason S. Shaik, PhD, is a Professor and the Director of the Lise Meitner-Minerva Center for Computational Quantum Chemistry in the Hebrew University in Jerusalem. He has been a Fulbright Fellow (1974-1979) and became a Fellow of the AAAS in 2005. Among his awards are the Israel Chemical Society Medal for the Outstanding Young Chemist (1987), the Alexander von Humboldt Senior Award in 1996-1999, the 2001 Kolthoff Award, the 2001 Israel Chemical Society Prize, and the 2007 Schrodinger Medal of WATOC. His research interests are in the use of quantum chemistry to develop paradigms that can pattern data and lead to the generation and solution of new problems. From 1981-1992, the main focus of his research was on valence bond theory and its relationship to MO theory, and during that time, he developed a general model of reactivity based on a blend of VB and MO elements. In 1994, he entered the field of oxidation and bond activation by metal oxo catalysts and enzymes, an area where he has contributed several seminal ideas (e.g., two-state reactivity) that led to resolution of major controversies and new predictions. 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.


Preface. 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 2 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? 5.1. Introduction. 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. 6.1. 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 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. 8.2. Applications. 8.3. A Summary. 9. Currently Available AB Initio Valence Bond Computational Methods and their Principles. 9.1. Introduction. 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. 10.1. Introduction. 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. Epilogue. Glossary. Index.

Product Details

  • publication date: 21/12/2007
  • ISBN13: 9780470037355
  • Format: Hardback
  • Number Of Pages: 316
  • ID: 9780470037355
  • weight: 610
  • ISBN10: 0470037350

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