Quantum Theory of Chemical Reactivity

Quantum Theory of Chemical Reactivity may be read without reference to the fact that it is actually the third of three volumes of a treatise on quantum chemistry, the science resulting from the implementation of mathematical laws in the realm of molecular populations. The first two volumes of the treatise, 'Fondement de la Chimie Tbeorique' and 'Structure Electrique des Molecules' were, like this third volume, originally published by Gauthier-Villars; Pergamon published the English translations of these two volumes. I am grateful to D. Reidel Publishing Company for translating the third volume of the treatise into English. Readers familiar with English rather than French now have access to the complete series. This treatise is a reflection of the courses I taught at the Sorbonne from 1950 until 1967 to students in their second cycle (3rd and 4th year) and third cycle (5th and 6th year) working towards a doctorate in this particular field. It is based on the reading of over a thousand articles, and is intended for students as well as for physical chemists, and chemists, research workers and engineers taking an interest in quantum chemistry for its own sake or for its application in industry, pharmacology and the life sciences. Reidel's initiative is particularly valuable because in my opinion Quantum Theory of Chemical Reactivity is the most important of the three volumes of the treatise. Doubtless for this reason only the third volume was published in Japanese by Baifukan, thanks to Professors Hayashi and Sohma.

Table of Contentes.- I. Basis of the Quantum Theory of the Chemical Reactivity Of Molecules.- 1. Introduction.- A. General Points Regarding Chemical Reactivity.- B. The Part Played by the Walls.- C. The Part Played by Impurities.- D. Part Played by Inert Gases and Solvents.- E. Analytical Balance and Mechanism of Reaction.- F. Levels of Vibration, Rotation and Conformations.- G. The Role of Quantum Chemistry.- 2. Equilibrium Constants in the Gaseous Phase.- A. Basic Formula.- B. Example of Para and Ortho Hydrogen.- C. Expression of the Macroscopic Thermodynamic Magnitudes as a Function of the Statistical Thermodynamic Magnitudes.- D. Regarding the Relationships of the Equilibrium Constants.- 3. Rate Constants of a Bimolecular Process in the Gaseous Phase.- A. The Hypothesis of a Transition State.- B. Expression of the Rate Constant of Decomposition of the Intermediate Complex.- C. Reaction Between a Hydrogen Atom and a Hydrogen Molecule.- D. Combination of Two Hydrogen Atoms.- 4. Rate Constants of the Monomolecular and Termolecular Processes in the Gaseous Phase.- A. The Combination of Oxygen and Nitrogen Peroxide.- B. A Few Remarks Regarding the Behaviour of the Unimolecular Processes.- References.- II. Intermolecular Forces, Interaction Between Non-Bonded Atoms, Conformational Equilibria.- 1. Introduction.- 2. Brief Analysis of the Methods of Calculation of Intermolecular Interactions.- A. Classification of Intermolecular Forces.- B. Electrostatic Forces.- C. Polarisation Forces.- D. Dispersion Forces.- E. Exclusion Forces.- F. On Forces by Charge Transfer.- G. The Hydrogen Bond.- H. Statistical Means and the Relative Importance of Molecular Interactions.- I. Empirical Treatment of Intermolecular Interactions.- 3. Interaction Between Unbonded Atoms.- A. Van der Waal’s Radii.- B. Conformations of acyclic Paraffins, Potential Barriers to Internal Rotation.- C. Conformational Equilibria in the Cyclane Series, Baeyer’s Tension, Cotton’s Effect.- D. Total Energy of Conjugated Molecules, Steric Effects, Spatial Conjugation.- References.- III. Equilibrium Constants of Reversible Reactions in Solution.- 1. Introduction.- 2. The Equilibrium Between the Triplet State and the Singlet State of Biradicaloid Molecules.- 3. Return to the Solvent Effect.- 4. Polarographic Semi-Wave Potential of Conjugated Molecules.- A. The Case of Hydrocarbons.- B. The Case of Other Conjugated Molecules.- 5. Other Oxidation-Reduction Equilibria.- A. Reduction Potential of Conjugated Hydrocarbons.- B. Oxidation Potential of Phenols.- C. Oxidation-Reduction Potential of Quinones.- D. Biochemical Applications.- 6. Strength of Acids and Bases.- A. Introduction.- B. Strength of Amino-Acids.- C. The Acid-Basic Character of Conjugated Hydrocarbons in the Ground State and in Their First Excited States.- D. Strength of Hetero-Atomic Conjugated Molecules in the Fundamental State.- E. The Effect of Electronic Excitation on the Acid/Basic Properties of Hetero-Atomic Conjugated Molecules.- 7. The Association Constants.- A. Association Between an Acceptor and a Proton Donor.- B. Other Examples.- 8. Tautomeric Equilibria: Application to the Study of the Mechanism of Mutations.- References.- IV. Rate Constants of a Few Reactions of Organic Chemistry.- 1. Introduction.- 2. A Few Examples of Studies of Rate Constants in the Field of Saturated Hydrocarbons and Their Derivatives.- A. Nucleophilic Substitutions SN2.- B. Nucleophilic Substitutions SN1.- C. Radical Reactions.- D. Chemistry of Radiations.- 3. A Few Examples of Studies of Rate Constants in the Field of Unsaturated Organic Molecules.- A. Substitution on an Alternating Conjugated Hydrocarbon, Localisation Energy and Method of Molecular Diagrams.- B. Other Examples of Substitutions on an Atom Belonging to the Delocalised System of a Conjugated Molecule.- C. Other Types of Substitution.- D. The Diene Synthesis and Addition Reactions.- E. Other Reactions.- F. Polymerisation Reactions.- 4. The Reactivity of Organic Molecules in an Excited Electronic State.- A. Introduction.- B. Electrophilic Substitutions.- C. Return to the Case of Butadiene.- D. Miscellaneous Studies.- References.- Index Of Names.- Index Of Subjects.