MODEL OF CAGE REACTIONS PROCEEDING THROUGH THE METASTABLE TERM

A model of cage reactions in the solid state is examined in which the Franck-Condon prohibition is overcome by crossing two parabolic terms of the same curvature. Since the final term is considered to be of short half life, its width is significant and there exists a transition probability. The effects on the reaction kinetics by the Markovian migration over the initial terms modulating resonance detuning and therefore the transition probability has been studied (the interaction is considered to be independent of the reaction coordinate). The case where the point of term crossing coincides with the minimum of the initial term is examined in detail. The reaction kinetics passes three stages with increasing migration frequency. The process develops non-exponentially in the slowest, quasi-static stage. The reaction kinetics and rate depend on the manner of migration in the migration-accelerated stage. Only in the kinetic stage when the migration is very fast does the traditional quasi-classical theory of electron migration hold which implies exponential reaction kinetics with the rate being independent of the energy migration. © 1979.