Relaxation hindrance in nonadiabatic cage reactions

In-cage reactions are considered in the model of two intersecting parabolic terms different in curvature and lifetime. Transitions between the terms are assumed (contact approximation) possible only at the crossing point that is reached due to diffusion along the terms. The non-exponential kinetics of nonactivated reactions and the rate constants of activated reactions following the exponential law have been calculated within the model proposed. The results obtained allow one to connect the nonadiabatic theory (weak interaction) with the Kramers adiabatic theory (strong interaction). It has been found that at strong friction in the nonadiabatic theory as well as in the Kramers theory, the reactions are hindered by relaxation, i.e. the limiting stage is either the reagent activation (diffusion along the first term), or the product relaxation (diffusion along the second term).     

The influence of the migration mechanism of approaching particles on the energy transfer between them

A way is proposed to experimentally solve the problem of the length of the jumps by which the particle diffusion in viscous solutions is realized. For that purpose it is necessary to measure the rate of impurity quenching of luminescence as a function of temperature and to choose among jumping, diffusion and mixed mechanisms of quenching. The measurements must be carried out at two concentrations: high (when the quenching is mainly static) and low (when the quenching is accelerated by motion).