Long-time kinetics of the excited-state association–dissociation reaction with different lifetimes

Abstract

We consider the long-time behaviour of the reversible diffusion-influenced reaction when A and C are immobile electronically excited states and B particles are in excess. A and C have different lifetimes. When C decays faster than A, the two leading terms of the asymptotic behaviour are obtained analytically by mapping this problem onto an effective irreversible reaction. The first term is exponential, and it coincides with that obtained from conventional rate equations with steady-state diffusion-influenced rate constants. The second term in the exponent is , as in the Smoluchowski irreversible kinetics.

Theory and Simulation of Diffusion-Controlled Michaelis−Menten Kinetics for a Static Enzyme in Solution

“…The pivotal observation here is that the MM mechanism is closely related to the excited-state ABC (ES-ABC) reaction with different lifetimes: ,, where k A and k C are the unimolecular decay rate constants of A and C, respectively, to their ground-state (GS). For a single A−B pair (the “geminate problem”), it is equivalent to the MM reaction scheme in eq 1.1 after setting k C = k p , and k A = 0.…”