A Chemist's Guide to Valence Bond Theory

, by Shaik, Sason S.; Hiberty, Philippe C.

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ISBN: 9780470037355 | 0470037350
Cover: Hardcover
Copyright: 12/4/2007

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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.

Preface	p. xiii
A Brief Story of Valence Bond Theory, Its Rivalry with Molecular Orbital Theory, Its Demise, and Resurgence	p. 1
Roots of VB Theory	p. 2
Origins of MO Theory and the Roots of VB-MO Rivalry	p. 5
One Theory is Up the Other is Down	p. 7
Mythical Failures of VB Theory: More Ground is Gained by MO Theory	p. 8
Are the Failures of VB Theory Real?	p. 12
The O[subscript 2] Failure	p. 12
The C[subscript 4]H[subscript 4] Failure	p. 13
The C[subscript 5]H[subscript 5 superscript +] Failure	p. 13
The Failure Associated with the Photoelectron Spectroscopy of CH[subscript 4]	p. 13
Valence Bond is a Legitimate Theory Alongside Molecular Orbital Theory	p. 14
Modern VB Theory: Valence Bond Theory is Coming of Age	p. 14
A Brief Tour Through Some Valence Bond Outputs and Terminology	p. 26
Valence Bond Output for the H[subscript 2] Molecule	p. 26
Valence Bond Mixing Diagrams	p. 32
Valence Bond Output for the HF Molecule	p. 33
Basic Valence Bond Theory	p. 40
Writing and Representing Valence Bond Wave Functions	p. 40
VB Wave Functions with Localized Atomic Orbitals	p. 40
Valence Bond Wave Functions with Semilocalized AOs	p. 41
Valence Bond Wave Functions with Fragment Orbitals	p. 42
Writing Valence Bond Wave Functions Beyond the 2e/2c Case	p. 43
Pictorial Representation of Valence Bond Wave Functions by Bond Diagrams	p. 45
Overlaps between Determinants	p. 45
Valence Bond Formalism Using the Exact Hamiltonian	p. 46
Purely Covalent Singlet and Triplet Repulsive States	p. 47
Configuration Interaction Involving Ionic Terms	p. 49
Valence Bond Formalism Using an Effective Hamiltonian	p. 49
Some Simple Formulas for Elementary Interactions	p. 51
The Two-Electron Bond	p. 51
Repulsive Interactions in Valence Bond Theory	p. 52
Mixing of Degenerate Valence Bond Structures	p. 53
Nonbonding Interactions in Valence Bond Theory	p. 54
Structural Coefficients and Weights of Valence Bond Wave Functions	p. 56
Bridges between Molecular Orbital and Valence Bond Theories	p. 56
Comparison of Qualitative Valence Bond and Molecular Orbital Theories	p. 57
The Relationship between Molecular Orbital and Valence Bond Wave Functions	p. 58
Localized Bond Orbitals: A Pictorial Bridge between Molecular Orbital and Valence Bond Wave Functions	p. 60
Appendix	p. 65
Normalization Constants, Energies, Overlaps, and Matrix Elements of Valence Bond Wave Functions	p. 65
Energy and Self-Overlap of an Atomic Orbital-Based Determinant	p. 66
Hamiltonian Matrix Elements and Overlaps between Atomic Orbital-Based Determinants	p. 68
Simple Guidelines for Valence Bond Mixing	p. 68
Exercises	p. 70
Answers	p. 74
Mapping Molecular Orbital-Configuration Interaction to Valence Bond Wave Functions	p. 81
Generating a Set of Valence Bond Structures	p. 81
Mapping a Molecular Orbital-Configuration Interaction Wave Function into a Valence Bond Wave Function	p. 83
Expansion of Molecular Orbital Determinants in Terms of Atomic Orbital Determinants	p. 83
Projecting the Molecular Orbital-Configuration Interaction Wave Function Onto the Rumer Basis of Valence Bond Structures	p. 85
An Example: The Hartree-Fock Wave Function of Butadiene	p. 86
Using Half-Determinants to Calculate Overlaps between Valence Bond Structures	p. 88
Exercises	p. 89
Answers	p. 90
Are the "Failures" of Valence Bond Theory Real?	p. 94
Introduction	p. 94
The Triplet Ground State of Dioxygen	p. 94
Aromaticity-Antiaromaticity in Ionic Rings C[subscript n]H[subscript n superscript +/-]	p. 97
Aromaticity/Antiaromaticity in Neutral Rings	p. 100
The Valence Ionization Spectrum of CH[subscript 4]	p. 104
The Valence Ionization Spectrum of H[subscript 2]O and the "Rabbit-Ear" Lone Pairs	p. 106
A Summary	p. 109
Exercises	p. 111
Answers	p. 112
Valence Bond Diagrams for Chemical Reactivity	p. 116
Introduction	p. 116
Two Archetypal Valence Bond Diagrams	p. 116
The Valence Bond State Correlation Diagram Model and Its General Outlook on Reactivity	p. 117
Construction of Valence Bond State Correlation Diagrams for Elementary Processes	p. 119
Valence Bond State Correlation Diagrams for Radical Exchange Reactions	p. 119
Valence Bond State Correlation Diagrams for Reactions between Nucleophiles and Electrophiles	p. 122
Generalization of Valence Bond State Correlation Diagrams for Reactions Involving Reorganization of Covalent Bonds	p. 124
Barrier Expressions Based on the Valence Bond State Correlation Diagram Model	p. 126
Some Guidelines for Quantitative Applications of the Valence Bond State Correlation Diagram Model	p. 128
Making Qualitative Reactivity Predictions with the Valence Bond State Correlation Diagram	p. 128
Reactivity Trends in Radical Exchange Reactions	p. 130
Reactivity Trends in Allowed and Forbidden Reactions	p. 132
Reactivity Trends in Oxidative-Addition Reactions	p. 133
Reactivity Trends in Reactions between Nucleophiles and Electrophiles	p. 136
Chemical Significance of the f Factor	p. 138
Making Stereochemical Predictions with the VBSCD Model	p. 138
Predicting Transition State Structures with the Valence Bond State Correlation Diagram Model	p. 140
Trends in Transition State Resonance Energies	p. 141
Valence Bond Configuration Mixing Diagrams: General Features	p. 144
Valence Bond Configuration Mixing Diagram with Ionic Intermediate Curves	p. 144
Valence Bond Configuration Mixing Diagrams for Proton-Transfer Processes	p. 145
Insights from Valence Bond Configuration Mixing Diagrams: One Electron Less-One Electron More	p. 146
Nucleophilic Substitution on Silicon: Stable Hypercoordinated Species	p. 147
Valence Bond Configuration Mixing Diagram with Intermediates Nascent from "Foreign States"	p. 149
The Mechanism of Nucleophilic Substitution of Esters	p. 149
The S[subscript RN]2 and S[subscript RN]2[superscript c] Mechanisms	p. 150
Valence Bond State Correlation Diagram: A General Model for Electronic Delocalization in Clusters	p. 153
What is the Driving Force for the D[subscript 6h] Geometry of Benzene, [sigma] or [pi]?	p. 154
Valence Bond State Correlation Diagram: Application to Photochemical Reactivity	p. 157
Photoreactivity in 3e/3c Reactions	p. 158
Photoreactivity in 4e/3c Reactions	p. 159
A Summary	p. 163
Exercises	p. 171
Answers	p. 176
Using Valence Bond Theory to Compute and Conceptualize Excited States	p. 193
Excited States of a Single Bond	p. 194
Excited States of Molecules with Conjugated Bonds	p. 196
Use of Molecular Symmetry to Generate Covalent Excited States Based on Valence Bond Theory	p. 197
Covalent Excited States of Polyenes	p. 209
A Summary	p. 212
Exercises	p. 215
Answers	p. 216
Spin Hamiltonian Valence Bond Theory and its Applications to Organic Radicals, Diradicals, and Polyradicals	p. 222
A Topological Semiempirical Hamiltonian	p. 223
Applications	p. 225
Ground States of Polyenes and Hund's Rule Violations	p. 225
Spin Distribution in Alternant Radicals	p. 227
Relative Stabilities of Polyenes	p. 228
Extending Ovchinnikov's Rule to Search for Bistable Hydrocarbons	p. 230
A Summary	p. 231
Exercises	p. 232
Answers	p. 234
Currently Available Ab Initio Valence Bond Computational Methods and their Principles	p. 238
Introduction	p. 238
Valence Bond Methods Based on Semilocalized Orbitals	p. 239
The Generalized Valence Bond Method	p. 240
The Spin-Coupled Valence Bond Method	p. 242
The CASVB Method	p. 243
The Generalized Resonating Valence Bond Method	p. 245
Multiconfiguration Valence Bond Methods with Optimized Orbitals	p. 246
Valence Bond Methods Based on Localized Orbitals	p. 247
Valence Bond Self-Consistent Field Method with Localized Orbitals	p. 247
The Breathing-Orbital Valence Bond Method	p. 249
The Valence Bond Configuration Interaction Method	p. 252
Methods for Getting Valence Bond Quantities from Molecular Orbital-Based Procedures	p. 253
Using Standard Molecular Orbital Software to Compute Single Valence Bond Structures or Determinants	p. 253
The Block-Localized Wave Function and Related Methods	p. 254
A Valence Bond Method with Polarizable Continuum Model	p. 255
Appendix	p. 257
Some Available Valence Bond Programs	p. 257
The TURTLE Software	p. 257
The XMVB Program	p. 257
The CRUNCH Software	p. 257
The VB2000 Software	p. 258
Implementations of Valence Bond Methods in Standard Ab Initio Packages	p. 258
Do Your Own Valence Bond Calculations-A Practical Guide	p. 271
Introduction	p. 271
Wave Functions and Energies for the Ground State of F[subscript 2]	p. 271
GVB, SC, and VBSCP Methods	p. 272
The BOVB Method	p. 276
The VBCI Method	p. 280
Valence Bond Calculations of Diabatic States and Resonance Energies	p. 281
Definition of Diabatic States	p. 282
Calculations of Meaningful Diabetic States	p. 282
Resonance Energies	p. 284
Comments on Calculations of VBSCDs and VBCMDs	p. 287
Appendix	p. 290
Calculating at the SD-BOVB Level in Low Symmetry Cases	p. 290
Epilogue	p. 304
Glossary	p. 306
Index	p. 311
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A Chemist's Guide to Valence Bond Theory

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