Theoretical Organic Chemistry (Volume 5) (Theoretical and Computational Chemistry, Volume 5)

✍ Scribed by C. Párkányi (editor)

• Publisher: Elsevier Science
• Year: 1997
• Tongue: English
• Leaves: 637
• Edition: 1
• Category: Library

✦ Synopsis

This volume is devoted to the various aspects of theoretical organic chemistry. In the nineteenth century, organic chemistry was primarily an experimental, empirical science. Throughout the twentieth century, the emphasis has been continually shifting to a more theoretical approach. Today, theoretical organic chemistry is a distinct area of research, with strong links to theoretical physical chemistry, quantum chemistry, computational chemistry, and physical organic chemistry.

The objective in this volume has been to provide a cross-section of a number of interesting topics in theoretical organic chemistry, starting with a detailed account of the historical development of this discipline and including topics devoted to quantum chemistry, physical properties of organic compounds, their reactivity, their biological activity, and their excited-state properties.

✦ Table of Contents

Theoretical Organic Chemistry
Copyright Page
Foreword
Acknowledgments
Table of Contents
Chapter 1. Theoretical Organic Chemistry: Looking Back in Wonder
1. Personal Preface
2. Introduction
3. The First Period (1850–1875)
4. Interlude 1
5. The Second Period (1910–1935)
6. Interlude 2
7. The Third Period
8. Epilogue
Chapter 2. Inter-Relations between VB & MO Theories for Organic II-Networks
1. Broad Motivation and Aim - Graph Theory
2. VB and MO Models
3. MO-Based Elaborations and Cross-Derivations
4. Hückel Rule
5. Polymers and Excitations
6. Prospects
Chapter 3. The Use of the Electrostatic Potential for Analysis and Prediction of Intermolecular Interactions
1. Introduction
2. Methodological Background
3. Analysis of Site-Specific Interactions
4. Analysis of Substituent Effects on Chemical Reactivity
5. Statistically-Based Interaction Indices
6. Summary
Chapter 4. Exploring Reaction Outcomes through the Reactivity-Selectivity Principle Estimated by Density Functional Theory Studies
1. Introduction
2. Computational Methodology
3. Basics for the Reactivity-Selectivity Approach
4. The Diels-Alder Reaction
5. Ring-Opening Reactions
6. Radical Reactions
7. Reactivity and Stability of Carbocations
8. Conclusion
Chapter 5. A Hardness and Softness Theory of Bond Energies and Chemical Reactivity
1. Introduction
2. Reactivity Parameters
3. Energy and Hardness Differences
4. Catalyzed Reactions and Reactions in Solution
5. Concluding Remarks
Chapter 6. Molecular Geometry as a Source of Chemical Information for π - Electron Compounds
Abstract
Introduction
1. Heat of Formation Derived from the Molecular Geometry: The Bond Energy Derived from CC Bond Lengths
2. Canonical Structure Weights Derived from the Molecular Geometry
3. Substituent Effect on the Molecular Geometry
4. Aromatic Character Derived from Molecular Geometry
5. Conclusions
Chapter 7. Average Local Ionization Energies: Significance and Applications
1. Introduction
2. Average Local Ionization Energies of Atoms
3. Average Local Ionization Energies of Molecules
4. Summary
Chapter 8. Intrinsic Proton Affinity of Substituted Aromatics
1. Introduction
2. Absolute Proton Affinities
3. Miscellaneous Applications of the Additivity Rule
4. Conclusion
Chapter 9. Dipole Moments of Aromatic Heterocycles
1. Introduction
2. Experimental Ground-State Dipole Moments
3. Calculated Ground-State Dipole Moments
4. Experimental Excited-State Dipole Moments
5. Calculated Excited-State Dipole Moments
6. Conclusion
Chapter 10. New Developments in the Analysis of Vibrational Spectra. On the Use of Adiabatic Internal Vibrational Modes
1. Introduction
2. The Concept of Localized Internal Vibrational Modes
3. The Basic Equations of Vibrational Spectroscopy
4. Previous Attempts of Defining Internal Vibrational Modes
5. Definition of Adiabatic Internal Modes
6. Definition of Adiabatic Internal Force Constant, Mass, and Frequency
7. Characterization of Normal Modes in Terms of Internal Vibrational Modes
8. Definition of Internal Mode Amplitudes A
9. Analysis of Vibrational Spectra in Terms of Adiabatic Internal Modes
10. Correlation of Vibrational Spectra of Different Molecules
11. Derivation of Bond Information from Vibrational Spectra
12. Adiabatic Internal Modes from Experimental Frequencies
13. A Generalization of Badger's Rule
14. Intensities of Adiabatic Internal Modes
15. Investigation of Reaction Mechanism with the Help of the CNM Analysis
16. Conclusions
Chapter 11. Atomistic Modeling of Enantioselection: Applications in Chiral Chromatography
Introduction
1. Stereochemistry
2. Chromatography
3. Molecular Modeling
4. Chiral Stationary Phase Systems
5. Modeling Enantioselective Binding
6. Type I CSPS
7. Type II CSPS
8. Type III CSPS
9. Type IV CSPS
10. Type V CSPS
Summary
Chapter 12. Theoretical Investigation of Carbon Nets and Molecules
1. Introduction
2. Infinite Planar Nets of sp2 -Hybridized Carbon Atoms
3. Infinite Nets of sp3-Hybridized Carbon Atoms
4. Infinite Nets with Both sp2- and sp3-Hybridized Carbon Atoms
5. Infinite Chains of sp-Hybridized Carbon Atoms
6. Molecules with sp2-Hybridized Carbon Atoms
7. Molecules with sp- and sp2-Hybridized Carbon Atoms
8. Conclusions: from Radioastronomy to Remedying Dangling Bonds Carbon Nets
Chapter 13. Protein Transmembrane Structure: Recognition and Prediction by Using Hydrophobicity Scales through Preference Functions
1. Introduction
2. Methods
3. Results
4. Discussion
Chapter 14. Polycyclic Aromatic Hydrocarbon Carcinogenicity: Theoretical Modelling and Experimental Facts
1. Introduction to Chemical Carcinogenesis
2. PAH Carcinogenicity and Theoretical Models
3. DNA Binding of Carcinogenic Hydrocarbon Metabolites
4. Hydrolysis and PAH Carcinogenicity
5. Molecular Modelling of Intercalated PAH Triol Carbocations
6. Conclusion
Chapter 15. Cycloaddition Reactions Involving Heterocyclic Compounds as Synthons in the Preparation of Valuable Organic Compounds. An Effective Combination of a Computational Study and Synthetic Applications of Heterocycle Transformations
1. Introduction
2. Computational Methodology
3. Diels-Alder Reactions with Five-Membered Heterocycles with One Heteroatom
4. Diels-Alder Reactions with Five-Membered Heterocycles with Two Heteroatoms
5. Diels-Alder Reactions with Five-Membered Heterocycles with Three Heteroatoms
6. Cycloaddition Reactions with Activated Heterocycles That Have Two or Three Heteroatoms
7. Conclusion
Chapter 16. Triplet Photoreactions; Structural Dependence of Spin-Orbit Coupling and Intersystem Crossing in Organic Biradicals
1. Introduction
2. Basic Theory
3. Spin-Orbit Coupling and Intersystem Crossing in Biradicals
4. Models for Spin-Orbit Coupling
5. Conclusions
Index