Journal of Chemical Physics, Vol.111, No.21, 9725-9730, 1999
Hydrodynamic effects in photoinduced electron transfer
The role of molecular motion in reversible charge transfer kinetics, which takes into account the hydrodynamic effect of molecular repulsion, has been considered in this work. The radial dependence of the diffusion coefficient, D(r), which accounts for disorder structure, is used. The hydrodynamic effect in infinite space is an essential factor. It decreases with the decrease of the acceptor concentration and of the forward charge transfer rate constant. It increases with the decrease of the viscosity of the solutions, in the case of high rate constants of the charge transfer. A comparison of this effect on the basis of two different theories has been made. The geometry of the molecular spectra influences the charge transfer process and the hydrodynamic effect. There exists a "false" hyperhydrodynamic effect as a result of the joint influence of the geometry of molecular spectra and of the r dependence of D(r).