Dynamic effect of ionic atmosphere on the kinetics of the elementary act of charge transfer reactions

A general method is developed enabling to take into account in a unified manner the dynamical behaviour of all the degrees of freedom of the system, including the movement of the reactants as a whole and the dynamics of the ionic atmosphere. The method relates the transition probability to the density matrices of the whole reacting system. The Franck—Condon approximation is not used. As an example, the homogeneous and electrochemical electron transfer reactions are considered. The dynamic effect of the ionic atmosphere on the charge transfer kinetics is shown to consist in that the configuration of the ionic atmosphere in the transition state is different from this in the equilibrium initial and final states and corresponds to intermediate charges of the reacting particles. The effect of image forces in the case of electrochemical reactions is taken into account.