Atomic Charges, Bond Properties, and Molecular Energies

Cover Page......Page 1
Title: ATOMIC CHARGES, BOND PROPERTIES, AND MOLECULAR ENERGIES......Page 3
ISBN 0470376228......Page 4
3 CORE AND VALENCE ELECTRONS......Page 5
8 POPULATION ANALYSIS......Page 6
13 SATURATED HYDROCARBONS......Page 7
BIBLIOGRAPHY......Page 8
PREFACE......Page 9
DEDICATION AND ACKNOWLEDGMENTS......Page 11
PART I CHARGE DISTRIBUTIONS......Page 13
1.1 THE BOND ENERGY MODEL......Page 15
1.2 SCOPE......Page 17
2.1 THE HARTREE–FOCK APPROXIMATION......Page 21
2.3 CONFIGURATION INTERACTION CALCULATIONS......Page 24
Examples......Page 26
3.1 INTRODUCTION......Page 29
3.2 ATOMIC CORE AND VALENCE REGIONS......Page 30
Computational Details......Page 35
3.3 THE VALENCE REGION ENERGY OF ATOMS......Page 37
Relationship between Core and Valence Region Energies......Page 38
Energy Formulas for Core and Valence Electrons......Page 39
Examples: Meaningful Core–Valence Partitioning......Page 42
Alternate Energy Formula......Page 45
3.4 SUMMARY......Page 46
4.1 MODEL......Page 47
4.2 THE CORE–VALENCE SEPARATION IN REAL SPACE......Page 48
Binding......Page 50
The Real-Space Core–Valence Partitioning......Page 51
4.3 FORMULA FOR THE VALENCE REGION ENERGY......Page 52
4.4 INTERFACE WITH THE ORBITAL MODEL......Page 55
Numerical Examples......Page 56
4.5 APPROXIMATION FOR THE VALENCE ENERGY......Page 58
Numerical Examples......Page 59
4.6 PERTURBATION OF THE VALENCE REGION......Page 61
4.7 SUMMARY......Page 62
5.1 INTRODUCTION......Page 65
5.2 THE INDUCTIVE EFFECTS......Page 66
5.3 MEANINGFUL ATOMIC CHARGES......Page 70
Charge–NMR Shift Correlations......Page 71
Auxiliary Relationships......Page 72
5.4 SELECTED REFERENCE NET ATOMIC CHARGES......Page 73
6.1 SCOPE......Page 77
6.3 MERITS OF CHARGE–SHIFT RELATIONSHIPS......Page 78
6.4 AROMATIC HYDROCARBONS......Page 80
Charge–Shift Correlations of Aromatic Hydrocarbons......Page 82
CARBON ATOMS......Page 84
6.6 RELATIONSHIPS INVOLVING OLEFINIC CARBONS......Page 86
6.7 CARBON BONDED TO NITROGEN OR OXYGEN......Page 88
6.8 CORRELATIONS INVOLVING N-15 NMR SHIFTS......Page 89
Alkylamines......Page 90
Isonitriles......Page 92
Substituted Pyridines and Diazines......Page 93
6.9 CORRELATIONS INVOLVING O-17 ATOMS......Page 95
6.10 SUMMARY......Page 98
CHAPTER 7 CHARGES AND IONIZATION POTENTIALS......Page 101
7.1 CONCLUSION......Page 103
8.1 THE STANDARD MULLIKEN FORMULA......Page 105
8.2 MODIFIED POPULATION ANALYSIS......Page 106
8.3 AN ADEQUATE APPROXIMATION......Page 107
8.4 CONCLUSIONS......Page 109
PART II CHEMICAL BONDS: ENERGY CALCULATIONS......Page 111
9.1 BASIC FORMULAS......Page 113
9.2 ZERO-POINT AND HEAT CONTENT ENERGIES......Page 115
Alkanes......Page 116
Alkenes......Page 118
Aromatic Hydrocarbons......Page 119
Carbonyl Compounds and Ethers......Page 120
9.3 CONCLUDING REMARKS......Page 122
10.1 SYNOPSIS......Page 125
10.2 NONBONDED INTERACTIONS......Page 127
10.3 REFERENCE BONDS......Page 129
10.4 BOND ENERGY: WORKING FORMULAS......Page 132
Final Energy Formulas......Page 136
Convenient Simplifictions......Page 137
10.5 BASIC THEORETICAL PARAMETERS......Page 138
10.6 SATURATED MOLECULES......Page 140
Saturated Hydrocarbons......Page 141
CHAPTER 11 THE CHEMICAL BOND: THEORY (II)......Page 145
11.1 VALENCE ATOMIC ORBITAL CENTROIDS......Page 146
Check Test: The Olefin......Page 148
Geometry Changes and Displacements of Charge Centroids......Page 150
11.2 UNSATURATED SYSTEMS......Page 153
Conjugation......Page 154
Reference Bonds......Page 156
The akl Parameters......Page 158
11.3 RECAPITULATION......Page 160
12.1 SCOPE......Page 163
12.2 THEORY......Page 164
12.3 NONBONDED INTERACTIONS......Page 168
12.4 SELECTED REORGANIZATIONAL ENERGIES......Page 169
The Carbon Skeleton of Alkanes......Page 170
Carbon–Hydrogen Bonds......Page 173
Applications......Page 175
Carbon–Nitrogen Bonds......Page 176
12.6 CONCLUSION......Page 178
PART III APPLICATIONS......Page 179
13.1 ACYCLIC ALKANES......Page 181
The Gauche Interactions......Page 183
Reference Charges......Page 189
General Formula for Olefin......Page 190
Dienes......Page 192
14.2 AROMATIC MOLECULES......Page 194
15.1 AMINES: CHARGES OF THE CARBON ATOMS......Page 201
15.2 NITROGEN CHARGES AND BOND ENERGIES......Page 202
Net Charges of the Nitrogen Atoms......Page 205
15.3 RESULTS......Page 206
16.1 ETHERS......Page 209
16.2 ALCOHOLS......Page 211
16.3 CARBONYL COMPOUNDS......Page 213
CHAPTER 17 PERSPECTIVES......Page 217
A.1 CHARGE–NMR SHIFT CORRELATIONS......Page 219
A.2 GENERAL ENERGY FORMULAS......Page 221
Dienes, Allenes, Alkynes and Benzene......Page 223
A.3 BOND ENERGY FORMULAS......Page 225
BIBLIOGRAPHY......Page 231
INDEX (with page links)......Page 243
Back Page......Page 247