A semiclassical theory of electron transfer reactions in Condon approximation and beyond

The effect of the modulation of the electronic wave functions by configurat ional fluctuations of the molecular environment on the kinetic parameters o f electron transfer reactions is discussed. A self-consistent algorithm for the calculation of the potential profile along the reaction coordinate of adiabatic electron transfer reactions is elaborated. A new formula for the transition probability of non-adiabatic electron transfer reactions is obta ined in an improved Condon approximation A regular method for the calculati on of non-Condon corrections is suggested. The importance of these effects for some specific biological and electrochemical electron transfer systems is discussed. (C) 2001 Elsevier Science B.V. All rights reserved.