Electronic Absorption Spectra and Geometry of Organic Molecules

Electronic Absorption Spectra and Geometry of Organic Molecules

An Application of Molecular Orbital Theory

1st Edition - January 1, 1967

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  • Author: Hiroshi Suzuki
  • eBook ISBN: 9780323145268

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Electronic Absorption Spectra and Geometry of Organic Molecules: An Application of Molecular Orbital Theory focuses on electronic absorption spectra of organic compounds and molecules. The book begins with the discussions on molecular spectra, electronic absorption spectra of organic compounds, and practical measures of absorption intensity. The text also focuses on molecular orbital theory and group theory. Molecular state functions; fundamental postulates of quantum theory; representation of symmetry groups; and symmetry operations and symmetry groups are described. The book also discusses shape of absorption bands and geometry of excited electronic states; effect of environment on electronic absorption spectra; and the application of simple LCAO MO method to simple π systems. An evaluation of the parameters used in simple LCAO MO method is presented. The text notes the usefulness and restrictions of simple LCAO MO method in the interpretation of electronic absorption spectra. The correlation between results of simple MO calculation and spectral data in aromatic hydrocarbons, and correlation between results of simple MO calculation and spectral data in conjugated linear polyenes are discussed. The book also looks at MO methods and the relations between electronic absorption spectra and geometry of molecules, biphenyl, styrene, and related compounds. The text is a good source of data for researchers and chemistry students who want to study electronic absorption spectra.

Table of Contents

  • Preface

    Chapter 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 Intensity

    Chapter 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 Method

    Chapter 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 Functions

    Chapter 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 Rules

    Chapter 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 States

    Chapter 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 State

    Chapter 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 Method

    Chapter 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 Hydrocarbons

    Chapter 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 Remarks

    Chapter 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 Hydrocarbons

    Chapter 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. Polyphenyls

    Chapter 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 Derivatives

    Chapter 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 Hexatriene

    Chapter 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 Bands

    Chapter 16. Conjugated Dienes and Polyenes

    16.1. Conjugated Dienes

    16.2. Conjugated Polyenes

    Chapter 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 Cyanines

    Chapter 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 System

    Chapter 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 Approximation

    Chapter 20. Advanced Composite-Molecule Method

    20.1. Principle

    20.2. Application

    Chapter 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 Compounds

    Chapter 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 Compounds

    Chapter 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. Disulfides

    Chapter 24. Interactions between Nonneighboring Atomic Orbitals

    24.1. Introduction

    24.2. Nonneighbor Interactions in Carbonyl Compounds

    24.3. Nonneighbor Interactions in Unsaturated Hydrocarbons

    Appendix. 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 References

    Author Index

    Subject Index

Product details

  • No. of pages: 582
  • Language: English
  • Copyright: © Academic Press 1967
  • Published: January 1, 1967
  • Imprint: Academic Press
  • eBook ISBN: 9780323145268

About the Author

Hiroshi Suzuki

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