Quantum theory of charge-transfer processes

Abstract

We provide a reformulation of the theory of charge-transfer processes in condensed media in terms of a density-matrix formalism. In contrast to previous developments we have also explicitly incorporated the dynamics of the relative motion of the reacting molecules and provided a general procedure for the calculation of the dielectric-permittivity function of the external solvent and incorporation of this quantity in the rate expressions, for both uniform and non-uniform media.

We have also reanalysed the character of protonic motion in proton-transfer reactions and derived a relationship between experimental second-order rate constants and the molar extinction coefficient for excess light absorption in a bimolecular collision complex.