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

The effect of the modulation of the electronic wave functions by configurational fluctuations of the molecular environment on the kinetic parameters of 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 obtained in an improved Condon approximation. A regular method for the calculation of non-Condon corrections is suggested. The importance of these effects for some specific biological and electrochemical electron transfer systems is discussed.