A Chemist's Guide to Valence Bond Theory [Hardcover]

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.

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 VB–MO 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 l“+