Quantum Theory of Chemical Reactions: II: Solvent Effect, Reaction Mechanisms, Photochemical Processes

ISBN-13: 9789401097185 / Angielski / Miękka / 2012 / 334 str.

R. Daudel; A. Pullman; L. Salem

Opis

The second volume of this treatise lS concerned with three important problems: a) environmental effects b) reaction mechanisms c) photochemical processes An important paper is devoted to the solvation problem. The local field representation of surrounding medium effect is analyzed and an application is made to the study of ambident reaction. A paper is devoted to the study of chemical reactivity in inert matrices and a theory of the effect of rare gas matrices on molecules is presented. Six papers are concerned with chemical reactions mechanisms. They are related to migration reactions, nucleophilic additions and electrophilic additions, and homogeneous catalytic reactions. Finally, some aspects of the photochemical processes are discussed. The evolution of electronically excited molecules is analyzed and the natural correlation method is presented. The role of Rydberg states' is photochemistry is suggested, we believe, for the first time. The sudden polarization in olefins is described in a critical way and a new phenomenon is presented: the pho- tochemical attachment of aliphatic hydrocarbons to polynuclear aromatic hydrocarbons. vii R. Daudel, A. Pullman, L. Salem, and A. Veillard (eds.;, Quantum Theory of Chemical Reactions, Volume II, vii. Copyright (c) 1980 by D. Reidel Publishing Company. THE SUPERMOLECULE APPROACH TO THE SOLVATION PROBLEM A. PULLMAN Institut de BioLogie Physico-Chimique Laboratoire de Biochimie Theorique, associe au C.N.R.S.

Spis treści

The Supermolecule Approach to the Solvation Problem.- Local Field Representation of Surrounding Medium Effects. From Liquid Solvent to Protein Core Effects.- The Effects of a Polarizable Environment Represented by the Generalized Born Formula in Self Consistent Quantum Chemical Calculations: Application to the Study of Ambident Reactions.- Chemical Reactivity in Inert Matrices.- Theory of Environmental Effects on Atoms and Molecules Trapped in Rare Gas Matrices.- Organometallic 1.2 Shift Type Migration Reactions.- A MO Treatment of the Regioselectivity of Nucleophilic Addition to ?-Enones.- An Electrophilic Addition Reaction in Solution: C2H4 + Cl2. Ab Initio Studies.- Theoretical Study of a Homogeneous Catalytic Reaction: The Chlorotris-(Triphenylphosphine)Rhodium(I)-Catalyzed Hydrogenation of Olefins.- Energy Surfaces in Quantum Chemistry.- Overlap in Binuclear Complexes: A Topological Approach of the Exchange Interaction.- The Evolution of Electronically Excited Molecules.- Study of Photochemical Reaction with Natural Correlation Method.- Theoretical Analysis of the Role of Rydberg States in the Photochemistry of Some Small Molecules.- Reappraisal of the Sudden Polarization in Olefins.- Photochemical Attachment of Aliphatic Hydrocarbons to Polynuclear Aromatic Hydrocarbons (PAH) in Rigid Alkane Matrices at 77K. Evidence for a Two-Photon Process Involving an Upper Excited Triplet State.- Index of Subjects.- Index of Names.