Page 13 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

Contents

Preface.................................................................. v
Acknowledgment and Personal Statement ................................ vii

Introduction ............................................................ ix
Chapter 1. Chemical Bonding and Molecular Structure ................. 1

Introduction ............................................................................................................ 1
1.1. Description of Molecular Structure Using Valence Bond Concepts............ 2
1.1.1. Hybridization ...................................................................................... 4
1.1.2. The Origin of Electron-Electron Repulsion....................................... 7
1.1.3. Electronegativity and Polarity ............................................................ 8
1.1.4. Electronegativity Equalization............................................................ 11
1.1.5. Differential Electronegativity of Carbon Atoms................................ 12
1.1.6. Polarizability, Hardness, and Softness ............................................... 14
1.1.7. Resonance and Conjugation ............................................................... 18
1.1.8. Hyperconjugation................................................................................ 22
1.1.9. Covalent and van der Waals Radii of Atoms .................................... 24
1.2. Molecular Orbital Theory and Methods........................................................ 26
1.2.1. The Hückel MO Method .................................................................... 27
1.2.2. Semiempirical MO Methods .............................................................. 32
1.2.3. Ab Initio Methods............................................................................... 32
1.2.4. Pictorial Representation of MOs for Molecules ................................ 35
1.2.5. Qualitative Application of MO Theory to Reactivity:
Perturbational MO Theory and Frontier Orbitals .............................. 41
1.2.6. Numerical Application of MO Theory............................................... 50
1.3. Electron Density Functionals......................................................................... 54
1.4. Representation of Electron Density Distribution .......................................... 57
1.4.1. Mulliken Population Analysis ............................................................ 60
1.4.2. Natural Bond Orbitals and Natural Population Analysis................... 61
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