The steady-state Greenʹs function theory in monomolecular reactions: II. Effects of solvent dynamics and non-equilibrium initial distributions in reactions on position-dependent transition regions Original Research Article

New theoretical methods are developed to analyze dynamical effects on the position-dependent, non-localized reaction transitions. Both time-dependent kinetics and average survival times are evaluated. Predicated on the steady-state Greenʹs function formalism introduced in Part I (Spirina and Doktorov, Chem. Phys., 203 (1995) 117), a consistent decoupling series approximation is introduced for the solution of dynamic equations. The conditions of its applicability are thoroughly analyzed. The approximation works well in the case of moderately narrow transition regions with weak-to-moderate electronic coupling. To compliment the decoupling procedure, the absorbing boundary approximation is introduced to cover the case of wider transition regions with strong electronic coupling. It is demonstrated that in the latter case, slow dynamics assure formation of the absorbing walls emerging from the center of the transition regions. Both methods require only straightforward evaluations as they successfully separate the surface dynamics from the reactive transitions. We present a consistent analysis of the major qualitative changes in the reaction rates induced by widening reaction regions. Special attention is paid to dynamic effects in reactions initiated by non-equilibrium distributions. A simple model for the description of dynamically smeared transition regions is also suggested and tested.