A Chemist's Guide to Valence Bond Theory

Modern valence bond theory and state-of-the-art methodologies

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.

Autorentext
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 Schrödinger 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.

Zusammenfassung
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.

Inhalt
PREFACE xiii 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 VBMO 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 C5H5þ 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 OrbitalConfiguration Interaction to Valence Bond Wave Functions 81 4.1 Generating a Set of Valence Bond Structures 81 4.2 Mapping a Molecular OrbitalConfiguration 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 OrbitalC…

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