Electronic Absorption Spectra and Geometry of Organic Molecules

PrefaceChapter 1. Introduction 1.1. Energy Levels of a Molecule and Molecular Spectra 1.2. Electronic Absorption Spectra of Organic Compounds 1.3. Wavelength, Wave Number, Energy, and Their Conversion Factors 1.4. Practical Measures of Absorption IntensityChapter 2. Molecular Orbital Theory 2.1. Fundamental Postulates of Quantum Theory 2.2. Molecular State Functions 2.3. The Method of Linear Combinations and the Variation Principle 2.4. The Perturbation MethodChapter 3. Group Theory 3.1. Symmetry Operations and Symmetry Groups 3.2. Representations of Symmetry Groups 3.3. Character Tables for Point Groups and Symmetry Properties of Molecules 3.4. Symmetry Properties of Products of FunctionsChapter 4. Absorption Intensity and Selection Rules 4.1. Transition Probability 4.2. Total Probability of an Electronic Transition and Its Distribution among Vibrational Components 4.3. Selection RulesChapter 5. Shape of Absorption Bands and Geometry of Excited Electronic States 5.1. Shape of Absorption Bands 5.2. Influence of Temperature and Environment upon the Band Shape 5.3. Geometry of Molecules in Excited Electronic StatesChapter 6. Effect of Environment upon Electronic Absorption Spectra 6.1. Introduction 6.2. Solvent Effect 6.3. Absorption Spectra of Molecular Complexes 6.4. Absorption Spectra of Molecules in the Solid StateChapter 7. Simple LCAO MO Method 7.1. Elements of Simple LCAO MO Method 7.2. The Pairing Property of π Orbitals of Alternant Hydrocarbons 7.3. Applications of Perturbation Theory in the Simple LCAO MO MethodChapter 8. Application of Simple LCAO MO Method to Some Simple π Systems 8.1. Simplification of Secular Determinants by the Use of Group Theory 8.2. Application of Simple LCAO MO Method to Butadiene 8.3. Application of Simple LCAO MO Method to Some Aromatic HydrocarbonsChapter 9. Evaluation of Parameters Used in Simple LCAO MO Method 9.1. Introduction 9.2. Evaluation of Coulomb Parameters 9.3. Evaluation of Resonance Parameters 9.4. Supplementary RemarksChapter 10. Usefulness and Limitations of Simple LCAO MO Method in Interpretation of Electronic Absorption Spectra 10.1. General 10.2. Singlet-Triplet Splitting 10.3. Effects of Configuration Interaction 10.4. Correlation between Results of Simple MO Calculation and Spectral Data in Conjugated Linear Polyenes 10.5. Correlation between Results of Simple MO Calculation and Spectral Data in Aromatic Hydrocarbons 10.6. Effects of Replacement of Carbon π Centers by Heteroatom π Centers and of Introduction of Nonmesomeric Substituents on Spectra of Conjugated Hydrocarbons Chapter 11. Advanced MO Methods 11.1. Introduction 11.2. Matrix Elements of the Total π-Electronic Hamiltonian between Antisymmetrized Electron Configuration Functions 11.3. The Semiempirical LCAO ASMO CI Method (The Pariser-Parr Method) 11.4. The Semiempirical SCF LCAO MO Method (The Pople Method) 11.5. Application of the Pariser-Parr Method to Even Alternant HydrocarbonsChapter 12. Relations between Electronic Absorption Spectra and Geometry of Molecules. Biphenyl and Related Compounds 12.1. Introduction 12.2. Biphenyl 12.3. o-Substituted Biphenyls 12.4. o,o'-Bridged Biphenyls 12.5. PolyphenylsChapter 13. Styrene and Related Compounds 13.1. Styrene and Its Alkylated Derivatives 13.2. 1-Phenylcyclohexene and Its Derivatives 13.3. 1,1-Diphenylethylene and Its Methylated DerivativesChapter 14. Stilbene and Related Compounds 14.1. Stilbene 14.2. Sterically Hindered Stilbene Derivatives 14.3. Tetraphenylethylene and Related Compounds 14.4. The Influence of Environment on the Spectra of Stilbene and of Related Compounds 14.5. Vinylogs of Stilbene and of Tetraphenylethylene 14.6. Biphenylene Derivatives of Ethylene, Butadiene, and HexatrieneChapter 15. Relations of the Intensity and Shape of Conjugation Bands to the Geometry of Conjugated Systems 15.1. Intensity of Conjugation Bands 15.2. Shape of Conjugation BandsChapter 16. Conjugated Dienes and Polyenes 16.1. Conjugated Dienes 16.2. Conjugated PolyenesChapter 17. Polymethine Dyes 17.1. Spectra of Odd-Membered Conjugated Systems 17.2. Steric Effects in Spectra of Symmetrical Cyanines 17.3. Steric Effects in Spectra of Highly Unsymmetrical CyaninesChapter 18. Nonplanar Aromatic Systems 18.1. General 18.2. Correlation of the Direction of the Wavelength Shift with the π-Bond Order of the Mainly Twisted Bond 18.3. Effects of the Distortion of the Whole Aromatic SystemChapter 19. Simple Composite-Molecule Method and a Classification of π-π* Transitions 19.1. Introduction 19.2. Simple Composite-Molecule Method 19.3. Classification of π-π* Transitions in Composite Systems 19.4. Classification of Composite Conjugated Systems and Steric Effects on π-π* Transitions of Various Types 19.5. Treatment of the Effect of a Methyl Substituent on Absorption Bands by the Perturbation Method 19.6. Mixing of Electron Configurations Formed of Orbitals of Fragments in the One-Electron ApproximationChapter 20. Advanced Composite-Molecule Method 20.1. Principle 20.2. ApplicationChapter 21. Carbonyl Compounds 21.1. The Carbonyl Group 21.2. Effects of Substituents on the Absorption Bands of the Carbonyl Group 21.3. Conjugated Dicarbonyl Compounds (α,ß-Dicarbonyls) 21.4. Vinyl-Carbonyl and Phenyl-Carbonyl Compounds 21.5. The Steric Effect in the Spectra of Conjugated Carbonyl CompoundsChapter 22. Nitrobenzene, Benzoic Acid, Aniline, and Related Compounds 22.1. Nitrobenzene and Related Compounds 22.2. Benzoic Acid and Related Compounds 22.3. Aniline and Related Compounds 22.4. Generalization of the Substituent Effects in the Spectra of Monosubstituted Benzenes—Weak and Strong Substituent Effects 22.5. Nitroanilines and Related CompoundsChapter 23. Azobenzenes and Related Compounds 23.1. The Azo Group 23.2. Aliphatic Azo Compounds 23.3. Azobenzenes 23.4. Azobenzene Analogs and Derivatives 23.5. Azoxy Compounds 23.6. Hydrazo Compounds 23.7. DisulfidesChapter 24. Interactions between Nonneighboring Atomic Orbitals 24.1. Introduction 24.2. Nonneighbor Interactions in Carbonyl Compounds 24.3. Nonneighbor Interactions in Unsaturated HydrocarbonsAppendix. Notation for Electronic Spectral Bands A.1. The Systems of Spectral Notation and Conventions Used in this Book A.2. Some Other Systems of Spectral Notation General ReferencesAuthor IndexSubject Index