Journal of Chemical Physics, Vol.104, No.8, 2976-2986, 1996
Solvent Structure and Hydrodynamic Effects in Photoinduced Electron-Transfer
A previously developed statistical mechanical theory describing photo-induced electron transfer and geminate recombination in liquid solutions has been modified to account for realistic finite-volume solvent effects. This work introduces physically important effects caused by the solvent which fundamentally affect the rates and spatial distribution of charge transfer events. The finite volume of solvent molecules gives rise to a nonuniform distribution of particles around an electron donor, which is incorporated into the theory by a two-particle radial distribution function (rdf). The Percus-Yevick solutions for the rdf can give numerically useful values for the solvent structure, g(R) although any form of g(R) can be used with the method. The nonuniform particle distribution significantly affects the electron transfer rates and the distribution of ion pairs formed by forward electron transfer, particularly at short times. In addition, finite solvent size affects the rate of relative diffusion between any donor-acceptor pair. These "hydrodynamic effects" slow down the interparticle diffusion rates when near contact, resulting in a major change in the long time behavior of photoexcited electron transfer systems. This work formally introduces the mathematical modifications to charge transfer theory necessary to account for the solvent structure and hydrodynamic effect and illustrates the results with model calculations. These calculations show that analysis of experiments with theories that do not include the rdf and hydrodynamic effects can result in significant errors in the interpretation of data.