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

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. Theoretical Organic Chemistry 4 Copyright Page 5 Foreword 6 Acknowledgments 7 Table of Contents 8 Chapter 1. Theoretical Organic Chemistry: Looking Back in Wonder 16 1. Personal Preface 16 2. Introduction 18 3. The First Period (1850–1875) 19 4. Interlude 1 21 5. The Second Period (1910–1935) 23 6. Interlude 2 27 7. The Third Period 29 8. Epilogue 35 Chapter 2. Inter-Relations between VB & MO Theories for Organic II-Networks 48 1. Broad Motivation and Aim - Graph Theory 48 2. VB and MO Models 50 3. MO-Based Elaborations and Cross-Derivations 53 4. Hückel Rule 56 5. Polymers and Excitations 59 6. Prospects 62 Chapter 3. The Use of the Electrostatic Potential for Analysis and Prediction of Intermolecular Interactions 66 1. Introduction 66 2. Methodological Background 66 3. Analysis of Site-Specific Interactions 80 4. Analysis of Substituent Effects on Chemical Reactivity 88 5. Statistically-Based Interaction Indices 96 6. Summary 102 Chapter 4. Exploring Reaction Outcomes through the Reactivity-Selectivity Principle Estimated by Density Functional Theory Studies 110 1. Introduction 110 2. Computational Methodology 111 3. Basics for the Reactivity-Selectivity Approach 111 4. The Diels-Alder Reaction 116 5. Ring-Opening Reactions 123 6. Radical Reactions 132 7. Reactivity and Stability of Carbocations 138 8. Conclusion 142 Chapter 5. A Hardness and Softness Theory of Bond Energies and Chemical Reactivity 150 1. Introduction 150 2. Reactivity Parameters 151 3. Energy and Hardness Differences 155 4. Catalyzed Reactions and Reactions in Solution 163 5. Concluding Remarks 165 Chapter 6. Molecular Geometry as a Source of Chemical Information for π - Electron Compounds 168 Abstract 168 Introduction 169 1. Heat of Formation Derived from the Molecular Geometry: The Bond Energy Derived from CC Bond Lengths 170 2. Canonical Structure Weights Derived from the Molecular Geometry 180 3. Substituent Effect on the Molecular Geometry 192 4. Aromatic Character Derived from Molecular Geometry 195 5. Conclusions 198 Chapter 7. Average Local Ionization Energies: Significance and Applications 204 1. Introduction 204 2. Average Local Ionization Energies of Atoms 205 3. Average Local Ionization Energies of Molecules 206 4. Summary 214 Chapter 8. Intrinsic Proton Affinity of Substituted Aromatics 218 1. Introduction 218 2. Absolute Proton Affinities 218 3. Miscellaneous Applications of the Additivity Rule 240 4. Conclusion 243 Chapter 9. Dipole Moments of Aromatic Heterocycles 248 1. Introduction 248 2. Experimental Ground-State Dipole Moments 250 3. Calculated Ground-State Dipole Moments 256 4. Experimental Excited-State Dipole Moments 260 5. Calculated Excited-State Dipole Moments 264 6. Conclusion 266 Chapter 10. New Developments in the Analysis of Vibrational Spectra. On the Use of Adiabatic Internal Vibrational Modes 274 1. Introduction 274 2. The Concept of Localized Internal Vibrational Modes 275 3. The Basic Equations of Vibrational Spectroscopy 278 4. Previous Attempts of Defining Internal Vibrational Modes 281 5. Definition of Adiabatic Internal Modes 282 6. Definition of Adiabatic Internal Force Constant, Mass, and Frequency 286 7. Characterization of Normal Modes in Terms of Internal Vibrational Modes 288 8. Definition of Internal Mode Amplitudes A 292 9. Analysis of Vibrational Spectra in Terms of Adiabatic Internal Modes 296 10. Correlation of Vibrational Spectra of Different Molecules 303 11. Derivation of Bond Information from Vibrational Spectra 312 12. Adiabatic Internal Modes from Experimental Frequencies 317 13. A Generalization of Badger's Rule 323 14. Intensities of Adiabatic Internal Modes 327 15. Investigation of Reaction Mechanism with the Help of the CNM Analysis 331 16. Conclusions 339 Chapter 11. Atomistic Modeling of Enantioselection: Applications in Chiral Chromatography 344 Introduction 344 1. Stereochemistry 345 2. Chromatography 347 3. Molecular Modeling 350 4. Chiral Stationary Phase Systems 350 5. Modeling Enantioselective Binding 351 6. Type I CSPS 351 7. Type II CSPS 369 8. Type III CSPS 378 9. Type IV CSPS 385 10. Type V CSPS 386 Summary 390 Chapter 12. Theoretical Investigation of Carbon Nets and Molecules 396 1. Introduction 396 2. Infinite Planar Nets of sp2 -Hybridized Carbon Atoms 396 3. Infinite Nets of sp3-Hybridized Carbon Atoms 400 4. Infinite Nets with Both sp2- and sp3-Hybridized Carbon Atoms 402 5. Infinite Chains of sp-Hybridized Carbon Atoms 406 6. Molecules with sp2-Hybridized Carbon Atoms 406 7. Molecules with sp- and sp2-Hybridized Carbon Atoms 413 8. Conclusions: from Radioastronomy to Remedying Dangling Bonds Carbon Nets 415 Chapter 13. Protein Transmembrane Structure: Recognition and Prediction by Using Hydrophobicity Scales through Preference Functions 420 1. Introduction 420 2. Methods 422 3. Results 429 4. Discussion 449 Chapter 14. Polycyclic Aromatic Hydrocarbon Carcinogenicity: Theoretical Modelling and Experimental Facts 462 1. Introduction to Chemical Carcinogenesis 462 2. PAH Carcinogenicity and Theoretical Models 465 3. DNA Binding of Carcinogenic Hydrocarbon Metabolites 476 4. Hydrolysis and PAH Carcinogenicity 487 5. Molecular Modelling of Intercalated PAH Triol Carbocations 492 6. Conclusion 502 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 516 1. Introduction 516 2. Computational Methodology 517 3. Diels-Alder Reactions with Five-Membered Heterocycles with One Heteroatom 517 4. Diels-Alder Reactions with Five-Membered Heterocycles with Two Heteroatoms 554 5. Diels-Alder Reactions with Five-Membered Heterocycles with Three Heteroatoms 564 6. Cycloaddition Reactions with Activated Heterocycles That Have Two or Three Heteroatoms 578 7. Conclusion 589 Chapter 16. Triplet Photoreactions; Structural Dependence of Spin-Orbit Coupling and Intersystem Crossing in Organic Biradicals 596 1. Introduction 596 2. Basic Theory 597 3. Spin-Orbit Coupling and Intersystem Crossing in Biradicals 602 4. Models for Spin-Orbit Coupling 615 5. Conclusions 621 Index 626 Content: Foreword Page v Cyril Párkányi Acknowledgments Page vi Theoretical organic chemistry: Looking back in wonder Original Research Article Pages 1-31 Jan J.C. Mulder Inter-relations between VB & MO theories for organic II-networks Original Research Article Pages 33-50 D.J. Klein The use of the electrostatic potential for analysis and prediction of intermolecular interactions Original Research Article Pages 51-93 Tore Brinck Exploring reaction outcomes through the reactivity-selectivity principle estimated by density functional theory studies Original Research Article Pages 95-133 Branko S. Jursic A hardness and softness theory of bond energies and chemical reactivity Original Research Article Pages 135-152 José L. Gázquez Molecular geometry as a source of chemical information for π-electron compounds Original Research Article Pages 153-187 Tadeusz Marek Krygowski, Michaκ Ksawery Cyrański Average local ionization energies: Significance and applications Original Research Article Pages 189-202 Jane S. Murray, Peter Politzer Intrinsic proton affinity of substituted aromatics Original Research Article Pages 203-231 Zvonimir B. Maksić, Mirjana Eckert-Maksić Dipole moments of aromatic heterocycles Original Research Article Pages 233-258 Cyril Párkányi, Jean-Jacques Aaron New developments in the analysis of vibrational spectra On the use of adiabatic internal vibrational modes Original Research Article Pages 259-327 Dieter Cremer, J. Andreas Larsson, Elfi Kraka Atomistic modeling of enantioselection: Applications in chiral chromatography Original Research Article Pages 329-379 Kenny B. Lipkowitz Theoretical investigation of carbon nets and molecules Original Research Article Pages 381-404 Alexandru T. Balaban Protein transmembrane structure: recognition and prediction by using hydrophobicity scales through preference functions Original Research Article Pages 405-445 Davor Juretić, Bono Lučić, Damir Zucić, Nenad Trinajstić Polycyclic aromatic hydrocarbon carcinogenicity: Theoretical modelling and experimental facts Original Research Article Pages 447-500 László von Szentpály, Ratna Ghosh 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 Original Research Article Pages 501-579 Branko S. Jursic Triplet photoreactions; Structural dependence of spin-orbit coupling and intersystem crossing in organic biradicals Original Research Article Pages 581-610 M. Klessinger Index Pages 611-622 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. This volume starts with a detailed account of the historical development of the discipline of organic chemistry and discussion devoted to quantum chemistry, physical properties of organic compounds, their reactivity, their biological activity, and their excited-state properties.