Excited-state reversible association-dissociation reaction:Renormalized Kinetic theory in configuration space

摘要

Kinetic theory of bimolecular reactions in liquid [M. Yang, S. Lee, and K. J. Shin, J. Chem. Phys. 108, 117, 8557, 9069 (1998)] is reformulated in the configuration space for the reversible pseudo-first-order association—dissociation reaction. By use of this formulation, we analyze the effect of finite excited-state lifetimes on the time dependence of the survival probabilities of reactant molecules in the presence of a competing bimolecular contact quenching process. In contrast with the excited-state reversible geminate recombination [I. V. Gopich and N. Agmon. J. Chem. Phys. 110, 10433 (1999)], the long time asymptotic behavior of the pseudo-first-order system shows different behavior. With the present results, we also reanalyze the experimental result [D. Huppert et al., Phys. Rev. Lett. 68, 3932 (1992)] qualitatively and make a suggestion for a possible reinterpretation of their experimental data.