Orbital Interactions in Chemistry, Second Edition

<p>Preface xi</p>
<p>About the Authors xiii</p>
<p>Chapter 1 Atomic and Molecular Orbitals 1</p>
<p>1.1 Introduction 1</p>
<p>1.2 Atomic Orbitals 1</p>
<p>1.3 Molecular Orbitals 7</p>
<p>Chapter 2 Concepts of Bonding and Orbital Interaction 15</p>
<p>2.1 Orbital Interaction Energy 15</p>
<p>2.2 Molecular Orbital Coefficients 20</p>
<p>2.3 The Two–Orbital Problem–Summary 24</p>
<p>2.4 Electron Density Distribution 26</p>
<p>Chapter 3 Perturbational Molecular Orbital Theory 32</p>
<p>3.1 Introduction 32</p>
<p>3.2 Intermolecular Perturbation 35</p>
<p>3.3 Linear H3, HF, and the Three–Orbital Problem 38</p>
<p>3.4 Degenerate Perturbation 43</p>
<p>Chapter 4 Symmetry 47</p>
<p>4.1 Introduction 47</p>
<p>4.2 Symmetry of Molecules 47</p>
<p>4.3 Representations of Groups 53</p>
<p>4.4 Symmetry Properties of Orbitals 59</p>
<p>4.5 Symmetry–Adapted Wavefunctions 62</p>
<p>4.6 Direct Products 65</p>
<p>4.7 Symmetry Properties, Integrals, and the Noncrossing Rule 67</p>
<p>4.8 Principles of Orbital Construction Using Symmetry Principles 69</p>
<p>4.9 Symmetry Properties of Molecular Vibrations 73</p>
<p>Chapter 5 Molecular Orbital Construction from Fragment Orbitals 78</p>
<p>5.1 Introduction 78</p>
<p>5.2 Triangular H3 78</p>
<p>5.3 Rectangular and Square Planar H4 82</p>
<p>5.4 Tetrahedral H4 84</p>
<p>5.5 Linear H4 86</p>
<p>5.6 Pentagonal H5 and Hexagonal H6 88</p>
<p>5.7 Orbitals of Cyclic Systems 91</p>
<p>Chapter 6 Molecular Orbitals of Diatomic Molecules and Electronegativity Perturbation 97</p>
<p>6.1 Introduction 97</p>
<p>6.2 Orbital Hybridization 98</p>
<p>6.3 Molecular Orbitals of Diatomic Molecules 99</p>
<p>6.4 Electronegativity Perturbation 105</p>
<p>6.5 Photoelectron Spectroscopy and Through–Bond Conjugation 112</p>
<p>Chapter 7 Molecular Orbitals and Geometrical Perturbation 123</p>
<p>7.1 Molecular Orbitals of AH2 123</p>
<p>7.2 Geometrical Perturbation 128</p>
<p>7.3 Walsh Diagrams 131</p>
<p>7.4 Jahn–Teller Distortions 134</p>
<p>7.5 Bond Orbitals and Photoelectron Spectra Of AH2 Molecules 141</p>
<p>Chapter 8 State Wavefunctions and State Energies 151</p>
<p>8.1 Introduction 151</p>
<p>8.2 The Molecular Hamiltonian and State Wavefunctions 152</p>
<p>8.3 Fock Operator 154</p>
<p>8.4 State Energy 156</p>
<p>8.5 Excitation Energy 157</p>
<p>8.6 Ionization Potential and Electron Affinity 160</p>
<p>8.7 Electron Density Distribution and Magnitudes of Coulomb and Exchange Repulsions 160</p>
<p>8.8 Low versus High Spin States 162</p>
<p>8.9 Electron–Electron Repulsion and Charged Species 164</p>
<p>8.10 Configuration Interaction 165</p>
<p>8.11 Toward More Quantitative Treatments 170</p>
<p>8.12 The Density Functional Method 174</p>
<p>Chapter 9 Molecular Orbitals of Small Building Blocks 179</p>
<p>9.1 Introduction 179</p>
<p>9.2 The AH System 179</p>
<p>9.3 Shapes of AH3 Systems 182</p>
<p>9.4 p–Bonding Effects of Ligands 190</p>
<p>9.5 The AH4 System 193</p>
<p>9.6 The AHn Series–Some Generalizations 198</p>
<p>Chapter 10 Molecules with Two Heavy Atoms 204</p>
<p>10.1 Introduction 204</p>
<p>10.2 A2H6 Systems 204</p>
<p>10.3 12–Electron A2H4 Systems 208</p>
<p>10.4 14–Electron AH2BH2 Systems 220</p>
<p>10.5 AH3BH2 Systems 223</p>
<p>10.6 AH3BH Systems 232</p>
<p>Chapter 11 Orbital Interactions through Space and through Bonds 241</p>
<p>11.1 Introduction 241</p>
<p>11.2 In–Plane s orbitals of Small Rings 241</p>
<p>11.3 Through–Bond Interaction 253</p>
<p>11.3.1 The Nature of Through–Bond Coupling 253</p>
<p>11.3.2 Other Through–Bond Coupling Units 256</p>
<p>11.4 Breaking a C––C Bond 258</p>
<p>Chapter 12 Polyenes and Conjugated Systems 272</p>
<p>12.1 Acyclic Polyenes 272</p>
<p>12.2 Huckel Theory 274</p>
<p>12.3 Cyclic Systems 277</p>
<p>12.4 Spin Polarization 285</p>
<p>12.5 Low– versus High–Spin States in Polyenes 289</p>
<p>12.6 Cross–Conjugated Polyenes 291</p>
<p>12.7 Perturbations of Cyclic Systems 294</p>
<p>12.8 Conjugation in Three Dimensions 303</p>
<p>Chapter 13 Solids 313</p>
<p>13.1 Energy Bands 313</p>
<p>13.2 Distortions in One–Dimensional Systems 328</p>
<p>13.3 Other One–Dimensional Systems 334</p>
<p>13.4 Two– and Three–Dimensional Systems 339</p>
<p>13.5 Electron Counting and Structure 350</p>
<p>13.6 High–Spin and Low–Spin Considerations 353</p>
<p>Chapter 14 Hypervalent Molecules 359</p>
<p>14.1 Orbitals of Octahedrally Based Molecules 359</p>
<p>14.2 Solid–State Hypervalent Compounds 373</p>
<p>14.3 Geometries of Hypervalent Molecules 383</p>
<p>Chapter 15&nbsp;Transition Metal Complexes: A Starting Point at the Octahedron 401</p>
<p>15.1 Introduction 401</p>
<p>15.2 Octahedral ML6 402</p>
<p>15.3 p–Effects in an Octahedron 406</p>
<p>15.4 Distortions from an Octahedral Geometry 416</p>
<p>15.5 The Octahedron in the Solid State 423</p>
<p>Chapter 16 Square Planar, Tetrahedral ML4 Complexes, and Electron Counting 436</p>
<p>16.1 Introduction 436</p>
<p>16.2 The Square Planar ML4 Molecule 436</p>
<p>16.3 Electron Counting 438</p>
<p>16.4 The Square Planar–Tetrahedral ML4 Interconversion 448</p>
<p>16.5 The Solid State 453</p>
<p>Chapter 17 Five Coordination 465</p>
<p>17.1 Introduction 465</p>
<p>17.2 The C4v ML5 Fragment 466</p>
<p>17.3 Five Coordination 468</p>
<p>17.4 Molecules Built Up from ML5 Fragments 480</p>
<p>17.5 Pentacoordinate Nitrosyls 489</p>
<p>17.6 Square Pyramids in The Solid State 492</p>
<p>Chapter 18 The C2v ML3 Fragment 503</p>
<p>18.1 Introduction 503</p>
<p>18.2 The Orbitals of A C2v ML3 Fragment 503</p>
<p>18.3 ML3–Containing Metallacycles 511</p>
<p>18.4 Comparison of C2v ML3 and C4v ML5 Fragments 518</p>
<p>Chapter 19 The ML2 and ML4 Fragments 527</p>
<p>19.1 Development of the C2v ML4 Fragment Orbitals 527</p>
<p>19.2 The Fe(CO)4 Story 529</p>
<p>19.3 Olefin–ML4 Complexes and M2L8 Dimers 533</p>
<p>19.4 The C2v ML2 Fragment 537</p>
<p>19.5 Polyene–ML2 Complexes 539</p>
<p>19.6 Reductive Elimination and Oxidative Addition 552</p>
<p>Chapter 20 Complexes of ML3, MCp and Cp2M 570</p>
<p>20.1 Derivation of Orbitals for a C3v ML3 Fragment 570</p>
<p>20.2 The CpM Fragment Orbitals 582</p>
<p>20.3 Cp2M and Metallocenes 592</p>
<p>20.4 Cp2MLn Complexes 595</p>
<p>Chapter 21 The Isolobal Analogy 616</p>
<p>21.1 Introduction 616</p>
<p>21.2 Generation of Isolobal Fragments 617</p>
<p>21.3 Caveats 621</p>
<p>21.4 Illustrations of the Isolobal Analogy 623</p>
<p>21.5 Reactions 634</p>
<p>21.6 Extensions 639</p>
<p>Chapter 22 Cluster Compounds 653</p>
<p>22.1 Types of Cluster Compounds 653</p>
<p>22.2 Cluster Orbitals 657</p>
<p>22.3 Wade s Rules 660</p>
<p>22.4 Violations 671</p>
<p>22.5 Extensions 677</p>
<p>Chapter 23 Chemistry on the Surface 691</p>
<p>23.1 Introduction 691</p>
<p>23.2 General Structural Considerations 693</p>
<p>23.3 General Considerations of Adsorption on Surfaces 696</p>
<p>23.4 Diatomics on a Surface 699</p>
<p>23.5 The Surface of Semiconductors 721</p>
<p>Chapter 24 Magnetic Properties 735</p>
<p>24.1 Introduction 735</p>
<p>24.2 The Magnetic Insulating State 736</p>
<p>24.3 Properties Associated with the Magnetic Moment 741</p>
<p>24.4 Symmetric Spin Exchange 745</p>
<p>24.5 Magnetic Structure 754</p>
<p>24.6 The Energy Gap in the Magnetic Energy Spectrum 763</p>
<p>24.7 Spin Orbit Coupling 766</p>
<p>24.8 What Appears versus What Is 778</p>
<p>24.9 Model Hamiltonians Beyond the Level of Spin Exchange 785</p>
<p>24.10 Summary Remarks 785</p>
<p>Problems 786</p>
<p>References 789</p>
<p>Appendix I Perturbational Molecular Orbital Theory 793</p>
<p>Appendix II Some Common Group Tables 803</p>
<p>Appendix III Normal Modes for Some Common Structural Types 808</p>
<p>Index 813</p>