Atomic Charges, Bond Properties, and Molecular Energies

ATOMIC CHARGES, BOND PROPERTIES, AND MOLECULAR ENERGIES......Page 4
CONTENTS......Page 8
PREFACE......Page 12
DEDICATION AND ACKNOWLEDGMENTS......Page 14
I CHARGE DISTRIBUTIONS......Page 16
1.1 The Bond Energy Model......Page 18
1.2 Scope......Page 20
2.1 The Hartree–Fock Approximation......Page 24
2.3 Configuration Interaction Calculations......Page 27
3.1 Introduction......Page 32
3.2 Atomic Core and Valence Regions......Page 33
3.3 The Valence Region Energy of Atoms......Page 40
3.4 Summary......Page 49
4.1 Model......Page 50
4.2 The Core–Valence Separation in Real Space......Page 51
4.3 Formula for the Valence Region Energy......Page 55
4.4 Interface with the Orbital Model......Page 58
4.5 Approximation for the Valence Energy......Page 61
4.6 Perturbation of the Valence Region......Page 64
4.7 Summary......Page 65
5.1 Introduction......Page 68
5.2 The Inductive Effects......Page 69
5.3 Meaningful Atomic Charges......Page 73
5.4 Selected Reference Net Atomic Charges......Page 76
6.1 Scope......Page 80
6.3 Merits of Charge–Shift Relationships......Page 81
6.4 Aromatic Hydrocarbons......Page 83
6.5 Relationships Involving sp(3) Carbon Atoms......Page 87
6.6 Relationships Involving Olefinic Carbons......Page 89
6.7 Carbon Bonded to Nitrogen or Oxygen......Page 91
6.8 Correlations Involving N-15 NMR Shifts......Page 92
6.9 Correlations Involving O-17 Atoms......Page 98
6.10 Summary......Page 101
7 CHARGES AND IONIZATION POTENTIALS......Page 104
7.1 Conclusion......Page 106
8.1 The Standard Mulliken Formula......Page 108
8.2 Modified Population Analysis......Page 109
8.3 An Adequate Approximation......Page 110
8.4 Conclusions......Page 112
II CHEMICAL BONDS: ENERGY CALCULATIONS......Page 114
9.1 Basic Formulas......Page 116
9.2 Zero-Point and Heat Content Energies......Page 118
9.3 Concluding Remarks......Page 125
10.1 Synopsis......Page 128
10.2 Nonbonded Interactions......Page 130
10.3 Reference Bonds......Page 132
10.4 Bond Energy: Working Formulas......Page 135
10.5 Basic Theoretical Parameters......Page 141
10.6 Saturated Molecules......Page 143
11 THE CHEMICAL BOND: THEORY (II)......Page 148
11.1 Valence Atomic Orbital Centroids......Page 149
11.2 Unsaturated Systems......Page 156
11.3 Recapitulation......Page 163
12.1 Scope......Page 166
12.2 Theory......Page 167
12.3 Nonbonded Interactions......Page 171
12.4 Selected Reorganizational Energies......Page 172
12.5 Applications......Page 173
12.6 Conclusion......Page 181
III APPLICATIONS......Page 182
13.1 Acyclic Alkanes......Page 184
13.2 Cycloalkanes......Page 186
14.1 Olefins......Page 192
14.2 Aromatic Molecules......Page 197
15.1 Amines: Charges of the Carbon Atoms......Page 204
15.2 Nitrogen Charges and Bond Energies......Page 205
15.3 Results......Page 209
16.1 Ethers......Page 212
16.2 Alcohols......Page 214
16.3 Carbonyl Compounds......Page 216
17 PERSPECTIVES......Page 220
A.1 Charge–NMR Shift Correlations......Page 222
A.2 General Energy Formulas......Page 224
A.3 Bond Energy Formulas......Page 228
BIBLIOGRAPHY......Page 234
INDEX......Page 246