Application of the integral encounter theory to the description of spin-selective processes

The description of homogeneous reactions in solutions is a very important problem of theoretical chemical physics. It should take into account stochastic motion of reactants in solution and distance-dependent reaction probability. Actually this is a very complicated many-body problem especially in the case of presence of reactants internal states. Fortunately, in the typical experimental situation the concentration of reactants is low, i.e. the volume fraction of reactants in solution is small. This assumption allows to develop theoretical approaches to the description of reacting systems. The consistent treatment of reaction processes in liquid phase leads to the so-called Integral Encounter Theory (IET)1–3) kinetic equations for the reactant concentrations. In the present work we employed IET for the consistent description of the photochemical radical-ion production with taking into account spin-selective character of recombination process and of the effect of degenerate electron exchange (DEE) in ESR spectra.