Quantum Theory of Chemical Reactivity

Publisher Summary In principle, two main methods can be used to predict the chemical reactivity of molecules, the collision theory and the transition state theory. The theoretical basis of the collision theory is certainly much more satisfactory than the basis of the transition state theory. But, the collision theory leads to very tedious calculations, and for this reason its practical interest is presently limited to the field of small molecules. On the contrary, the transition theory has been used extensively to predict the chemical reactivity of both small and large molecules, and thus is discussed in this chapter. The basis of the transition state theory is described for the case of small molecules. It is known that following this way, the constant rate of a chemical reaction appears to be the product of an equilibrium constant, and of the rate of decomposition of the intermediate complex. The chapter also presents the calculation of equilibrium constants. Many examples are given, including conformational equilibria, oxydo-reduction potential, and base strength. The role of the various factors involved is analyzed. Various examples of calculation of rate constants are outlined. These discussions are concerned with Walden inversion, substitutions on a carbon atom belonging to an aromatic ring, and photochemical reactions.

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