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Preface | |

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Symmetry and Stereochemistry | |

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Purpose | |

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Definition of a Group | |

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Molecular Point Groups | |

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Schoenflies Notation | |

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Interrelations of Symmetry Elements | |

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Type Classification | |

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Isomerism and Measurements | |

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Stereoisomerism of Molecules | |

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Stereotopic Relationships of Groups in Molecules | |

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Asymmetric Synthesis and Stereochemistry | |

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NMR and Stereochemistry | |

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Symmetry and Structural Parameters | |

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Note on Hybridization | |

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Symmetry and Orbitals | |

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Atomic Orbitals | |

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Molecular and Group Orbitals | |

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In What Combination? | |

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Molecular Orbital Theory | |

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Introduction | |

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Electronic Schrodinger Equation (A.1) | |

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Fock Equations (A.42) | |

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The Basis Set (STO-3G, 6-31G*, and All That) | |

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Orbital Energies and Orbitals | |

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Representation of MOs | |

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Total Energies and the Hartree-Fock Limit | |

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Successes and Failures of Hartree-Fock Theory | |

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Beyond Hartree-Fock | |

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Density Functional Theory | |

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Geometry Optimization | |

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Normal Coordinates and Harmonic Frequency Analysis | |

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Zero Point Vibrational Energies | |

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Orbital Interaction Theory | |

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Relationship to Hartree-Fock Equations | |

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Huckel Approximation | |

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Orbital Energies and Total Electronic Energy | |

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Case Study of a Two-Orbital Interaction | |

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Case 1: [varepsilon subscript A] = [varepsilon subscript B], S[subscript AB] = 0 | |

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Case 2: [varepsilon subscript A] = [varepsilon subscript B], S[subscript AB] ] 0, S[subscript AB] [angle quoation mark left] 1 | |

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Case 3: [varepsilon subscript A] ] [varepsilon subscript B], S[subscript AB] = 0 | |

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Case 4: [varepsilon subscript A] ] [varepsilon subscript B], S[subscript AB] ] 0 | |

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Effect of Overlap | |

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Energetic Effect of Overlap | |

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Orbital Effect of Overlap | |

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First Look at Bonding | |

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Relationship to Perturbation Theory | |

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Generalizations for Intermolecular Interactions | |

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Energy and Charge Distribution Changes from Orbital Interaction | |

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Four-Electron, Two-Orbital Interaction | |

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Three-Electron, Two-Orbital Interaction | |

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Two-Electron, Two-Orbital Interaction | |

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One-Electron, Two-Orbital Interaction | |

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Zero-Electron, Two-Orbital Interaction | |

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Interactions between Molecules: Many Electrons, Many Orbitals | |

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General Principles Governing the Magnitude of h[subscript AB] and S[subscript AB] | |

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Interactions of MOs | |

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Electrostatic Effects | |

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Group Orbitals | |

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Zero-Coordinated Atoms | |

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Monocoordinated Atoms | |

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Dicoordinated Atoms | |

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Tricoordinated Atoms | |

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Tetracoordinated Atoms | |

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Assumptions for Application of Qualitative MO Theory | |

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Example: Carbonyl Group | |

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Construction of Interaction Diagram | |

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Interpretation of Interaction Diagram | |

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Chemical Reactivity | |

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Why Does It Work and When Might it Not? | |

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Sigma Bonds and Orbital Interaction Theory | |

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C--X [sigma] Bonds: X = C, N, O, F and X = F, Cl, Br, I | |

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[sigma] Bonds: Homolytic versus Heterolytic Cleavage | |

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Heterolytic Cleavage of [sigma] Bonds Involving C or H | |

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Homolytic Cleavage of [sigma] Bonds Involving C or H | |

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Homonuclear [sigma] Bonds C--C, N--N, O--O, F--F, Cl--Cl, Br--Br, and I--I | |

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Interactions of [sigma] Bonds | |

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[sigma] Bonds as Electron Donors or Acceptors | |

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[sigma] Bonds as Electron Acceptors | |

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As a [sigma] Acceptor | |

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As a [pi] Acceptor | |

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[sigma] Bonds as Electron Donors | |

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As a [sigma] Donor | |

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As a [pi] Donor | |

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Bonding in Cyclopropane | |

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Simple Huckel Molecular Orbital Theory | |

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Simple Huckel Assumptions | |

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Charge and Bond Order in SHMO Theory: (S[subscript AB] = 0, One Orbital per Atom | |

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Electron Population and Net Charge of Center A | |

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Bond Order between Centers A and B | |

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Factors Governing Energies of MOs: SHMO Theory | |

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Reference Energy and Energy Scale | |

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Heteroatoms in SHMO Theory | |

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Effect of Coordination Number on [alpha] and [beta] | |

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Hybridization at C in Terms of [alpha] and [beta] | |

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Gross Classification of Molecules on the Basis of MO Energies | |

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Reactions and Properties of [pi] Bonds | |

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Reactions of Olefins (Alkenes) | |

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Effect of X: Substituents | |

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Effect of Z Substituents | |

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Effect of "C" Substituents | |

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Effect of Distortion of Molecular Skeleton | |

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Alkynes | |

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[pi] Bonds to and between Higher Row Elements | |

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[pi] Bonds to Silicon, Phosphorus, and Sulfur | |

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Reactive Intermediates | |

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Reactive Intermediates [CH subscript 3 superscript +], [CH subscript 3 superscript -], [CH subscript 3 superscript .], and [:CH subscript 2] | |

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Carbocations | |

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Intermolecular Reactions of Carbocations | |

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Intramolecular Reactions of Carbocations | |

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Silyl Cations | |

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Carbanions | |

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Carbon Free Radicals | |

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Carbenes | |

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Nitrenes and Nitrenium Ions | |

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Nitrenes | |

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Nitrenium Ions | |

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Carbonyl Compounds | |

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Reactions of Carbonyl Compounds | |

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Electrophilic Attack on a Carbonyl Group | |

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Basicity and Nucleophilicity of the Oxygen Atom | |

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Nucleophilic Attack on a Carbonyl Group | |

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Amide Group | |

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Thermodynamic Stability of Substituted Carbonyl Groups | |

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Nucleophilic Substitution Reactions | |

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Nucleophilic Substitution at Saturated Carbon | |

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Unimolecular Nucleophilic Substitution S[subscript N]1 | |

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Bimolecular Nucleophilic Substitution S[subscript N]2 | |

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Another Description of the S[subscript N]2 Reaction: VBCM Model | |

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Bonds to Hydrogen | |

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Hydrogen Bonds and Proton Abstraction Reactions | |

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Hydrogen Bonds | |

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Symmetrical and Bifurcated Hydrogen Bonds | |

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Proton Abstraction Reactions | |

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E2 Elimination Reaction | |

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E1cB Mechanism Reaction | |

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E1 Elimination Reaction | |

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Reaction with Electrophiles: Hydride Abstraction and Hydride Bridging | |

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Activation by [pi] Donors (X: and "C" Substituents) | |

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Hydride Abstraction | |

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Hydride Bridges | |

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Reaction with Free Radicals: Hydrogen Atom Abstraction and One- or Three-Electron Bonding | |

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Hydrogen-Bridged Radicals | |

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Hydrogen Atom Transfer | |

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Aromatic Compounds | |

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Reactions of Aromatic Compounds | |

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Cyclic [pi] Systems by Simple Huckel MO Theory | |

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Aromaticity in [sigma]-Bonded Arrays? | |

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Reactions of substituted Benzenes | |

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Electrophilic Substitutions | |

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Effect of Substituents on Substrate Reactivity | |

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Electrophilic Attack on X:-Substituted Benzenes | |

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Electrophilic Attack on Z-Substituted Benzenes | |

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Electrophilic Attack on "C"-Substituted Benzenes | |

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Electrophilic Attack on N Aromatics: Pyrrole and Pyridine | |

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Nucleophilic Substitutions | |

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Effect of Substituents on Substrate Reactivity | |

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Nucleophilic Attack on Z-Substituted Benzenes | |

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Nucleophilic Attack on N Aromatics: Pyrrole and Pyridine | |

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Nucleophilic Substitution by Proton Abstraction | |

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Pericyclic Reactions | |

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General Considerations | |

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Cycloadditions and Cycloreversions | |

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Stereochemical Considerations | |

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Electrocyclic Reactions | |

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Stereochemical Considerations | |

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Cheletropic Reactions | |

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Stereochemical Considerations | |

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Sigmatropic Rearrangements | |

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Stereochemical Considerations | |

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Component Analysis (Allowed or Forbidden?) | |

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Rule for Component Analysis | |

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Diels-Alder Reaction | |

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Cope Rearrangement | |

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1,3-Dipolar Cycloaddition Reactions | |

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Organometallic Compounds | |

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Transition Metals | |

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Ligands in Transition Metal Complexes | |

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Orbitals in Transition Metal Bonding | |

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Orbital Energies | |

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Valence Orbitals of Reactive Metal Complexes | |

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Six Valence Orbitals of Tricoordinated Metal | |

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Five Valence Orbitals of Tetracoordinated Metal | |

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Four Valence Orbitals of Pentacoordinated Structure | |

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Transition Metals and C--H or H--H Sigma Bonds | |

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More About C Ligands in Transition Metal Complexes | |

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Chelating Ligands | |

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Organic [pi]-Bonded Molecules as Ligands | |

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Transition Metal Bonding to Alkenes: Zeise's Salt | |

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Agostic Interaction | |

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Ziegler-Natta Polymerization | |

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Oxidative Addition to H--H and C--H Bonds | |

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Orbital and State Correlation Diagrams | |

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General Principles | |

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Woodward-Hoffman Orbital Correlation Diagrams | |

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Cycloaddition Reactions | |

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Electrocyclic Reactions | |

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Cheletropic Reactions | |

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Photochemistry from Orbital Correlation Diagrams | |

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Limitations of Orbital Correlation Diagrams | |

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State Correlation Diagrams | |

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Electronic States from MOs | |

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Rules for Correlation of Electronic States | |

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Example: Carbene Addition to an Olefin | |

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Photochemistry | |

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Photoexcitation | |

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Jablonski Diagram | |

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Fate of Excited Molecule in Solution | |

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Dauben-Salem-Turro Analysis | |

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Norrish Type II Reaction of Carbonyl Compounds | |

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Norrish Type I Cleavage Reaction of Carbonyl Compounds | |

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Derivation of Hartree-Fock Theory | |

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Electronic Hamiltonian Operator | |

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Electronic Schrodinger Equation | |

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Expectation Values | |

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Many-Electron Wave Function | |

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Electronic Hartree-Fock Energy | |

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Variation of E[subscript HF] | |

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LCAO Solution of Fock Equations | |

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Integrals | |

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The Basis Set (STO-3G, 6-31G*, and All That) | |

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Interpretation of Solutions of HF Equations | |

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Orbital Energies and Total Electronic Energy | |

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Restricted Hartree-Fock Theory | |

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Mulliken Population Analysis | |

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Dipole Moments | |

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Total Energies | |

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Configuration Energies | |

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Post-Hartree-Fock Methods | |

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Configuration Interaction Theory | |

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Excited States from CI Calculations | |

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Many-Body Perturbation Theory | |

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Rayleigh-Schrodinger Perturbation Theory | |

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Moller-Plesset Perturbation Theory | |

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Density Functional Theory | |

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Exercises | |

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Chapter 1 | |

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Chapter 2 and Appendix A | |

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Chapter 3 | |

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Chapter 4 | |

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Chapter 5 | |

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Chapter 6 | |

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Chapter 7 | |

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Chapter 8 | |

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Chapter 9 | |

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Chapter 10 | |

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Chapter 11 | |

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Chapter 12 | |

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Chapter 13 | |

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Chapter 14 | |

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Chapter 15 | |

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Miscellaneous | |

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References and Notes | |

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Index | |