Models for Bonding in Chemistry

Models for Bonding in Chemistry......Page 5
Contents......Page 9
Preface......Page 13
1.1 MATRICES AND SYSTEMS OF LINEAR EQUATIONS......Page 17
1.2 PROPERTIES OF EIGENVALUES AND EIGENVECTORS......Page 22
1.3 VARIATIONAL APPROXIMATIONS......Page 26
1.4 ATOMIC UNITS......Page 31
1.5 THE ELECTRON DISTRIBUTION IN MOLECULES......Page 33
1.6 EXCHANGE-OVERLAP DENSITIES AND THE CHEMICAL BOND......Page 35
Part 1: Short-range Interactions......Page 43
2 The Chemical Bond......Page 45
2.1 AN ELEMENTARY MOLECULAR ORBITAL MODEL......Page 46
2.2 BOND ENERGIES AND PAULI REPULSIONS IN HOMONUCLEAR DIATOMICS......Page 50
2.2.3 The Helium Molecular Ion He+2 (N = 3)......Page 51
2.2.4 The Helium Molecule He2 (N = 4)......Page 52
2.3 MULTIPLE BONDS......Page 53
2.3.1 σ2π2 Description of the Double Bond......Page 54
2.3.2 B 2 1 B 2 2 Bent (or Banana) Description of the Double Bond......Page 56
2.3.3 Hybridization Effects......Page 58
2.3.4 Triple Bonds......Page 62
2.4 THE THREE-CENTRE DOUBLE BOND IN DIBORANE......Page 63
2.5 THE HETEROPOLAR BOND......Page 65
2.6.1 The Molecular Orbital Model of Directed Valency......Page 71
2.6.2 Analysis of the MO Bond Energy......Page 74
2.7 sp-HYBRIDIZATION EFFECTS IN FIRST-ROW HYDRIDES......Page 76
2.7.1 The Methane Molecule......Page 77
2.7.2 The Hydrogen Fluoride Molecule......Page 80
2.7.3 The Water Molecule......Page 91
2.7.4 The Ammonia Molecule......Page 103
2.8 DELOCALIZED BONDS......Page 112
2.8.2 The Allyl Radical......Page 114
2.8.3 The Butadiene Molecule......Page 116
2.8.4 The Cyclobutadiene Molecule......Page 118
2.8.5 The Benzene Molecule......Page 120
2.9.1 The Second Derivative of the H€uckel Energy......Page 124
2.9.2 The Set of Three Coulson’s Orthogonal Hybrids......Page 125
2.9.3 Calculation of Coefficients of Real MOs for Benzene......Page 126
3 An Introduction to Bonding in Solids......Page 135
3.1 THE LINEAR POLYENE CHAIN......Page 136
3.1.1 Butadiene N = 4......Page 138
3.2 THE CLOSED POLYENE CHAIN......Page 139
3.2.1 Benzene N = 6......Page 142
3.3 A MODEL FOR THE ONE-DIMENSIONAL CRYSTAL......Page 147
3.4 ELECTRONIC BANDS IN CRYSTALS......Page 149
3.5 INSULATORS, CONDUCTORS, SEMICONDUCTORS AND SUPERCONDUCTORS......Page 154
3.6 APPENDIX: THE TRIGONOMETRIC IDENTITY......Page 159
Part 2: Long-Range Interactions......Page 161
4.1 INTRODUCTION......Page 163
4.2 ELEMENTS OF RAYLEIGH–SCHRÖDINGER (RS) PERTURBATION THEORY......Page 165
4.3 MOLECULAR INTERACTIONS......Page 167
4.3.1 Non-expanded Energy Corrections up to Second Order......Page 168
4.3.2 Expanded Energy Corrections up to Second Order......Page 169
4.4 THE TWO-STATE MODEL OF LONG-RANGE INTERACTIONS......Page 173
4.5 THE van der WAALS INTERACTIONS......Page 175
4.5.1 Atom–Atom Dispersion......Page 177
4.5.2 Atom–Linear Molecule Dispersion......Page 178
4.5.3 Atom–Linear Dipolar Molecule10 Induction......Page 179
4.6 THE C6 DISPERSIONCOEFFICIENT FOR THE H–H INTERACTION......Page 181
4.7 THE van der WAALS BOND......Page 183
4.8 THE KEESOM INTERACTION......Page 185
5 The Hydrogen Bond......Page 193
5.1 A MOLECULAR ORBITAL MODEL OF THE HYDROGEN BOND......Page 194
5.2 ELECTROSTATIC INTERACTIONS AND THE HYDROGEN BOND......Page 195
5.2.1 The Hydrogen Fluoride Dimer (HF)2......Page 198
5.2.2 The Water Dimer (H2O)2......Page 201
5.3 THE ELECTROSTATIC MODEL OF THE HYDROGEN BOND......Page 202
5.4 THE Rg–HF HETERODIMERS......Page 213
References......Page 217
Author Index......Page 225
Subject Index......Page 229