Orbital Interactions In Chemistry -- Contents -- Preface -- About the Authors -- Chapter 1: Atomic and Molecular Orbitals -- 1.1 Introduction -- 1.2 Atomic Orbitals -- 1.3 Molecular Orbitals -- Problems -- References -- Chapter 2: Concepts of Bonding and Orbital Interaction -- 2.1 Orbital Interaction Energy -- 2.1.1 Degenerate Interaction -- 2.1.2 Nondegenerate Interaction -- 2.2 Molecular Orbital Coefficients -- 2.2.1 Degenerate Interaction -- 2.2.2 Nondegenerate Interaction -- 2.3 The Two-Orbital Problem-Summary -- 2.4 Electron Density Distribution -- Problems -- References -- Chapter 3: Perturbational Molecular Orbital Theory -- 3.1 Introduction -- 3.2 Intermolecular Perturbation -- 3.3 Linear H3, HF, and the Three-Orbital Problem -- 3.4 Degenerate Perturbation -- Problems -- References -- Chapter 4: Symmetry -- 4.1 Introduction -- 4.2 Symmetry of Molecules -- 4.3 Representations of Groups -- 4.4 Symmetry Properties of Orbitals -- 4.5 Symmetry-Adapted Wavefunctions -- 4.6 Direct Products -- 4.7 Symmetry Properties, Integrals, and the Noncrossing Rule -- 4.8 Principles of Orbital Construction Using Symmetry Principles -- 4.9 Symmetry Properties of Molecular Vibrations -- Problems -- References -- Chapter 5: Molecular Orbital Construction from Fragment Orbitals -- 5.1 Introduction -- 5.2 Triangular H3 -- 5.3 Rectangular and Square Planar H4 -- 5.4 Tetrahedral H4 -- 5.5 Linear H4 -- 5.6 Pentagonal H5 and Hexagonal H6 -- 5.7 Orbitals of Cyclic Systems -- Problems -- References -- Chapter 6: Molecular Orbitals of Diatomic Molecules and Electronegativity Perturbation -- 6.1 Introduction -- 6.2 Orbital Hybridization -- 6.3 Molecular Orbitals of Diatomic Molecules -- 6.4 Electronegativity Perturbation -- 6.5 Photoelectron Spectroscopy and Through-Bond Conjugation -- Problems -- References -- Chapter 7: Molecular Orbitals and Geometrical Perturbation.

7.1 Molecular Orbitals of AH2 -- 7.2 Geometrical Perturbation -- 7.3 Walsh Diagrams -- 7.4 Jahn-Teller Distortions -- 7.4.1 First-Order Jahn-Teller Distortion -- 7.4.2 Second-Order Jahn-Teller Distortion -- 7.4.3 Three-Center Bonding -- 7.5 Bond Orbitals and Photoelectron Spectra Of AH2 Molecules -- Problems -- References -- Chapter 8: State Wavefunctions and State Energies -- 8.1 Introduction -- 8.2 The Molecular Hamiltonian and State Wavefunctions -- 8.3 Fock Operator -- 8.4 State Energy -- 8.5 Excitation Energy -- 8.6 Ionization Potential and Electron Affinity -- 8.7 Electron Density Distribution and Magnitudes of Coulomb and Exchange Repulsions -- 8.8 Low versus High Spin States -- 8.9 Electron-Electron Repulsion and Charged Species -- 8.10 Configuration Interaction -- 8.11 Toward More Quantitative Treatments -- 8.12 The Density Functional Method -- Problems -- References -- Chapter 9: Molecular Orbitals of Small Building Blocks -- 9.1 Introduction -- 9.2 The AH System -- 9.3 Shapes of AH3 Systems -- 9.4 π-Bonding Effects of Ligands -- 9.5 The AH4 System -- 9.6 The AHn Series-Some Generalizations -- Problems -- References -- Chapter 10: Molecules with Two Heavy Atoms -- 10.1 Introduction -- 10.2 A2H6 Systems -- 10.3 12-Electron A2H4 Systems -- 10.3.1 Sudden Polarization -- 10.3.2 Substituent Effects -- 10.3.3 Dimerization and Pyramidalization of AH2 -- 10.4 14-Electron AH2BH2 Systems -- 10.5 AH3BH2 Systems -- 10.6 AH3BH Systems -- Problems -- References -- Chapter 11: Orbital Interactions through Space and through Bonds -- 11.1 Introduction -- 11.2 In-Plane s orbitals of Small Rings -- 11.2.1 Cyclopropane -- 11.2.2 Cyclobutane -- 11.3 Through-Bond Interaction -- 11.3.1 The Nature of Through-Bond Coupling -- 11.3.2 Other Through-Bond Coupling Units -- 11.4 Breaking A C-C Bond -- Problems -- References -- Chapter 12: Polyenes and Conjugated Systems.

12.1 Acyclic Polyenes -- 12.2 Hückel Theory -- 12.3 Cyclic Systems -- 12.4 Spin Polarization -- 12.5 Low- versus High-Spin States in Polyenes -- 12.6 Cross-Conjugated Polyenes -- 12.7 Perturbations of Cyclic Systems -- 12.8 Conjugation in Three Dimensions -- Problems -- References -- Chapter 13: Solids -- 13.1 Energy Bands -- 13.2 Distortions in One-Dimensional Systems -- 13.3 Other One-Dimensional Systems -- 13.4 Two- and Three-Dimensional Systems -- 13.5 Electron Counting and Structure -- 13.6 High-Spin and Low-Spin Considerations -- Problems -- References -- Chapter 14: Hypervalent Molecules -- 14.1 Orbitals of Octahedrally Based Molecules -- 14.2 Solid-State Hypervalent Compounds -- 14.3 Geometries of Hypervalent Molecules -- Problems -- References -- Chapter 15: Transition Metal Complexes: A Starting Point at the Octahedron -- 15.1 Introduction -- 15.2 Octahedral ML6 -- 15.3 π-Effects in an Octahedron -- 15.4 Distortions from an Octahedral Geometry -- 15.5 The Octahedron in the Solid State -- Problems -- References -- Chapter 16: Square Planar, Tetrahedral ML4 Complexes, and Electron Counting -- 16.1 Introduction -- 16.2 The Square Planar ML4 Molecule -- 16.3 Electron Counting -- 16.4 The Square Planar-Tetrahedral ML4 Interconversion -- 16.5 The Solid State -- Problems -- References -- Chapter 17: Five Coordination -- 17.1 Introduction -- 17.2 The C4v ML5 Fragment -- 17.3 Five Coordination -- 17.4 Molecules Built Up from ML5 Fragments -- 17.5 Pentacoordinate Nitrosyls -- 17.6 Square Pyramids in The Solid State -- Problems -- References -- Chapter 18: The C2v ML3 Fragment -- 18.1 Introduction -- 18.2 The Orbitals of A C2v ML3 Fragment -- 18.3 ML3-Containing Metallacycles -- 18.4 Comparison of C2v ML3 and C4v ML5 Fragments -- Problems -- References -- Chapter 19: The ML2 and ML4 Fragments -- 19.1 Development of the C2v ML4 Fragment Orbitals.

19.2 The Fe(CO)4 Story -- 19.3 Olefin-ML4 Complexes and M2L8 Dimers -- 19.4 The C2v ML2 Fragment -- 19.5 Polyene-ML2 Complexes -- 19.6 Reductive Elimination and Oxidative Addition -- Problems -- References -- Chapter 20: Complexes of ML3, MCp and Cp2M -- 20.1 Derivation of Orbitals for a C3v ML3 Fragment -- 20.2 The CpM Fragment Orbitals -- 20.3 Cp2M and Metallocenes -- 20.4 Cp2MLn Complexes -- Problems -- References -- Chapter 21: The Isolobal Analogy -- 21.1 Introduction -- 21.2 Generation of Isolobal Fragments -- 21.3 Caveats -- 21.4 Illustrations of the Isolobal Analogy -- 21.5 Reactions -- 21.6 Extensions -- Problems -- References -- Chapter 22: Cluster Compounds -- 22.1 Types of Cluster Compounds -- 22.2 Cluster Orbitals -- 22.3 Wade's Rules -- 22.4 Violations -- 22.5 Extensions -- Problems -- References -- Chapter 23: Chemistry on the Surface -- 23.1 Introduction -- 23.2 General Structural Considerations -- 23.3 General Considerations of Adsorption on Surfaces -- 23.4 Diatomics on a Surface -- 23.5 The Surface of Semiconductors -- Problems -- References -- Chapter 24: Magnetic Properties -- 24.1 Introduction -- 24.2 The Magnetic Insulating State -- 24.2.1 Electronic Structures -- 24.2.2 Factors Affecting the Effective On-Site Repulsion -- 24.2.3 Effect of Spin Arrangement on the Band Gap -- 24.3 Properties Associated With the Magnetic Moment -- 24.3.1 The Magnetic Moment -- 24.3.2 Magnetization -- 24.3.3 Magnetic Susceptibility -- 24.3.4 Experimental Investigation of Magnetic Energy Levels -- 24.4 Symmetric Spin Exchange -- 24.4.1 Mapping Analysis for a Spin Dimer -- 24.4.2 Through-Space and Through-Bond Orbital Interactions Leading to Spin Exchange -- 24.4.3 Mapping Analysis Based on Broken-Symmetry States -- 24.5 Magnetic Structure -- 24.5.1 Spin Frustration and Noncollinear Spin Arrangement -- 24.5.2 Long-Range Antiferromagnetic Order.

24.5.3 Ferromagnetic and Ferromagnetic-Like Transitions -- 24.5.4 Typical Cases Leading to Ferromagnetic Interaction -- 24.5.5 Short-Range Order -- 24.6 The Energy Gap in the Magnetic Energy Spectrum -- 24.6.1 Spin Gap and Field-Induced Magnetic Order -- 24.6.2 Magnetization Plateaus -- 24.7 Spin-Orbit Coupling -- 24.7.1 Spin Orientation -- 24.7.2 Single-Ion Anisotropy -- 24.7.3 Uniaxial Magnetism versus Jahn-Teller Instability -- 24.7.4 The Dzyaloshinskii-Moriya Interaction -- 24.7.5 Singlet-Triplet Mixing Under Spin-Orbit Coupling -- 24.8 What Appears versus What Is -- 24.8.1 Idle Spin in Cu3(OH)4SO4 -- 24.8.2 The FM-AFM versus AFM-AFM Chain -- 24.8.3 Diamond Chains -- 24.8.4 Spin Gap Behavior of a Two-Dimensional Square Net -- 24.9 Model Hamiltonians Beyond the Level of Spin Exchange -- 24.10 Summary Remarks -- Problems -- References -- Appendix I: Perturbational Molecular Orbital Theory -- Appendix II: Some Common Group Tables -- Appendix III: Normal Modes for Some Common Structural Types -- Index.