화학공학소재연구정보센터
Journal of Physical Chemistry, Vol.98, No.13, 3424-3431, 1994
Analytical Treatment of Nonexponential Electron-Transfer Coupled to Intramolecular and Medium Modes
A many-mode model for electron transfer is developed. The electron transfer is coupled to the classical solvent dynamics and to a molecular subsystem, consisting of many internal modes which form a dense manifold of states for electron transfer in the inverted region. The fluctuations of the solvent coordinate are treated as an uncorrelated stochastic process. For the limit of slow fluctuations it is shown that a transition from a solvent-controlled transfer to a solvent-independent one occurs as a function of the free energy of reaction. The mode predicts a nonexponential electron-transfer kinetics of the intermediate region.