Diffusion-influenced excited-state reversible transfer reactions, A*+B ⇄ C* +D, with two different lifetimes: Theories and simulations

Abstract

We report accurate Brownian simulation results for the kinetics of the pseudo-first-order diffusion-influenced excited-state reversible transfer reaction A* +B⇌ C* +D with two different lifetimes using two different propagation algorithms. The results are used to test approximate solutions for this many-particle problem. Available theories fail when one of the two reactions or (decay) rate constants is large. To remedy this situation, we develop two uniform approximations, which are based on introducing a generalized Smoluchowski term into the relaxation-time approximation. The best of these is the extended unified theory of reversible target reactions, which reduces correctly in all limits and exhibits superior agreement with simulations. © 2005 American Institute of Physics.