THE STEADY-STATE GREENS-FUNCTION THEORY IN MONOMOLECULAR REACTIONS - II - EFFECTS OF SOLVENT DYNAMICS AND NONEQUILIBRIUM INITIAL DISTRIBUTIONS IN REACTIONS ON POSITION-DEPENDENT TRANSITION REGIONS

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. Predicate d on the steady-state Green's function formalism introduced in Part I (Spirina and Doktorov, Chem. Phys., 203 (1995) 117), a consistent deco upling 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 transi tion regions with weak-to-moderate electronic coupling. To compliment the decoupling procedure, the absorbing boundary approximation is intr oduced to cover the case of wider transition regions with strong elect ronic coupling. It is demonstrated that in the latter case, slow dynam ics assure formation of the absorbing walls emerging from the center o f the transition regions. Both methods require only straightforward ev aluations as they successfully separate the surface dynamics from the reactive transitions. We present a consistent analysis of the major qu alitative changes in the reaction rates induced by widening reaction r egions. Special attention is paid to dynamic effects in reactions init iated by non-equilibrium distributions. A simple model for the descrip tion of dynamically smeared transition regions is also suggested and t ested. (C) 1998 Elsevier Science B.V. All rights reserved.