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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 | |