화학공학소재연구정보센터
Journal of Chemical Physics, Vol.107, No.22, 9361-9369, 1997
Dwell time of nonadiabatic electron transfer reaction: Solvent dynamic effects
We study the tunneling behavior in a curve crossed parabolic free energy surface with friction via a dwell time method. The dwell time is defined as the difference of the mean first passage time between the delocalized and the localized nonadiabatic electron transfer reactions. The equation of motion of nonadiabatic electron transfer reaction in the condensed phase obeys a semiclassical Zusman equation [L. D. Zusman, Chem. Phys. 40, 295 (1980)]. By using the eigenfunction expansion method, the dwell time and the tunneling probability density at short time are solved numerically. It is shown that the dwell time of the nonadiabatic electron transfer reaction between two parabolic free energy surfaces depends on the delocalization width (or diabatic width) and the force difference at the crossing point. This dwell time is proportional to (longitudinal dielectric relaxation time)/(electronic coupling constant)(2). (C) 1997 American Institute of Physics.