Preface xi

About the Authors xiii

Chapter 1 Atomic and Molecular Orbitals 1

1.1 Introduction 1

1.2 Atomic Orbitals 1

1.3 Molecular Orbitals 7

Chapter 2 Concepts of Bonding and Orbital Interaction 15

2.1 Orbital Interaction Energy 15

2.2 Molecular Orbital Coefficients 20

2.3 The Two-Orbital Problem-Summary 24

2.4 Electron Density Distribution 26

Chapter 3 Perturbational Molecular Orbital Theory 32

3.1 Introduction 32

3.2 Intermolecular Perturbation 35

3.3 Linear H3, HF, and the Three-Orbital Problem 38

3.4 Degenerate Perturbation 43

Chapter 4 Symmetry 47

4.1 Introduction 47

4.2 Symmetry of Molecules 47

4.3 Representations of Groups 53

4.4 Symmetry Properties of Orbitals 59

4.5 Symmetry-Adapted Wavefunctions 62

4.6 Direct Products 65

4.7 Symmetry Properties, Integrals, and the Noncrossing Rule 67

4.8 Principles of Orbital Construction Using Symmetry Principles 69

4.9 Symmetry Properties of Molecular Vibrations 73

Chapter 5 Molecular Orbital Construction from Fragment Orbitals 78

5.1 Introduction 78

5.2 Triangular H3 78

5.3 Rectangular and Square Planar H4 82

5.4 Tetrahedral H4 84

5.5 Linear H4 86

5.6 Pentagonal H5 and Hexagonal H6 88

5.7 Orbitals of Cyclic Systems 91

Chapter 6 Molecular Orbitals of Diatomic Molecules and Electronegativity Perturbation 97

6.1 Introduction 97

6.2 Orbital Hybridization 98

6.3 Molecular Orbitals of Diatomic Molecules 99

6.4 Electronegativity Perturbation 105

6.5 Photoelectron Spectroscopy and Through-Bond Conjugation 112

Chapter 7 Molecular Orbitals and Geometrical Perturbation 123

7.1 Molecular Orbitals of AH2 123

7.2 Geometrical Perturbation 128

7.3 Walsh Diagrams 131

7.4 Jahn-Teller Distortions 134

7.5 Bond Orbitals and Photoelectron Spectra Of AH2 Molecules 141

Chapter 8 State Wavefunctions and State Energies 151

8.1 Introduction 151

8.2 The Molecular Hamiltonian and State Wavefunctions 152

8.3 Fock Operator 154

8.4 State Energy 156

8.5 Excitation Energy 157

8.6 Ionization Potential and Electron Affinity 160

8.7 Electron Density Distribution and Magnitudes of Coulomb and Exchange Repulsions 160

8.8 Low versus High Spin States 162

8.9 Electron-Electron Repulsion and Charged Species 164

8.10 Configuration Interaction 165

8.11 Toward More Quantitative Treatments 170

8.12 The Density Functional Method 174

Chapter 9 Molecular Orbitals of Small Building Blocks 179

9.1 Introduction 179

9.2 The AH System 179

9.3 Shapes of AH3 Systems 182

9.4 p-Bonding Effects of Ligands 190

9.5 The AH4 System 193

9.6 The AHn Series-Some Generalizations 198

Chapter 10 Molecules with Two Heavy Atoms 204

10.1 Introduction 204

10.2 A2H6 Systems 204

10.3 12-Electron A2H4 Systems 208

10.4 14-Electron AH2BH2 Systems 220

10.5 AH3BH2 Systems 223

10.6 AH3BH Systems 232

Chapter 11 Orbital Interactions through Space and through Bonds 241

11.1 Introduction 241

11.2 In-Plane s orbitals of Small Rings 241

11.3 Through-Bond Interaction 253

11.3.1 The Nature of Through-Bond Coupling 253

11.3.2 Other Through-Bond Coupling Units 256

11.4 Breaking a C--C Bond 258

Chapter 12 Polyenes and Conjugated Systems 272

12.1 Acyclic Polyenes 272

12.2 Huckel Theory 274

12.3 Cyclic Systems 277

12.4 Spin Polarization 285

12.5 Low- versus High-Spin States in Polyenes 289

12.6 Cross-Conjugated Polyenes 291

12.7 Perturbations of Cyclic Systems 294

12.8 Conjugation in Three Dimensions 303

Chapter 13 Solids 313

13.1 Energy Bands 313

13.2 Distortions in One-Dimensional Systems 328

13.3 Other One-Dimensional Systems 334

13.4 Two- and Three-Dimensional Systems 339

13.5 Electron Counting and Structure 350

13.6 High-Spin and Low-Spin Considerations 353

Chapter 14 Hypervalent Molecules 359

14.1 Orbitals of Octahedrally Based Molecules 359

14.2 Solid-State Hypervalent Compounds 373

14.3 Geometries of Hypervalent Molecules 383

Chapter 15 Transition Metal Complexes: A Starting Point at the Octahedron 401

15.1 Introduction 401

15.2 Octahedral ML6 402

15.3 p-Effects in an Octahedron 406

15.4 Distortions from an Octahedral Geometry 416

15.5 The Octahedron in the Solid State 423

Chapter 16 Square Planar, Tetrahedral ML4 Complexes, and Electron Counting 436

16.1 Introduction 436

16.2 The Square Planar ML4 Molecule 436

16.3 Electron Counting 438

16.4 The Square Planar-Tetrahedral ML4 Interconversion 448

16.5 The Solid State 453

Chapter 17 Five Coordination 465

17.1 Introduction 465

17.2 The C4v ML5 Fragment 466

17.3 Five Coordination 468

17.4 Molecules Built Up from ML5 Fragments 480

17.5 Pentacoordinate Nitrosyls 489

17.6 Square Pyramids in The Solid State 492

Chapter 18 The C2v ML3 Fragment 503

18.1 Introduction 503

18.2 The Orbitals of A C2v ML3 Fragment 503

18.3 ML3-Containing Metallacycles 511

18.4 Comparison of C2v ML3 and C4v ML5 Fragments 518

Chapter 19 The ML2 and ML4 Fragments 527

19.1 Development of the C2v ML4 Fragment Orbitals 527

19.2 The Fe(CO)4 Story 529

19.3 Olefin-ML4 Complexes and M2L8 Dimers 533

19.4 The C2v ML2 Fragment 537

19.5 Polyene-ML2 Complexes 539

19.6 Reductive Elimination and Oxidative Addition 552

Chapter 20 Complexes of ML3, MCp and Cp2M 570

20.1 Derivation of Orbitals for a C3v ML3 Fragment 570

20.2 The CpM Fragment Orbitals 582

20.3 Cp2M and Metallocenes 592

20.4 Cp2MLn Complexes 595

Chapter 21 The Isolobal Analogy 616

21.1 Introduction 616

21.2 Generation of Isolobal Fragments 617

21.3 Caveats 621

21.4 Illustrations of the Isolobal Analogy 623

21.5 Reactions 634

21.6 Extensions 639

Chapter 22 Cluster Compounds 653

22.1 Types of Cluster Compounds 653

22.2 Cluster Orbitals 657

22.3 Wade’s Rules 660

22.4 Violations 671

22.5 Extensions 677

Chapter 23 Chemistry on the Surface 691

23.1 Introduction 691

23.2 General Structural Considerations 693

23.3 General Considerations of Adsorption on Surfaces 696

23.4 Diatomics on a Surface 699

23.5 The Surface of Semiconductors 721

Chapter 24 Magnetic Properties 735

24.1 Introduction 735

24.2 The Magnetic Insulating State 736

24.3 Properties Associated with the Magnetic Moment 741

24.4 Symmetric Spin Exchange 745

24.5 Magnetic Structure 754

24.6 The Energy Gap in the Magnetic Energy Spectrum 763

24.7 Spin–Orbit Coupling 766

24.8 What Appears versus What Is 778

24.9 Model Hamiltonians Beyond the Level of Spin Exchange 785

24.10 Summary Remarks 785

Problems 786

References 789

Appendix I Perturbational Molecular Orbital Theory 793

Appendix II Some Common Group Tables 803

Appendix III Normal Modes for Some Common Structural Types 808

Index 813