Role of Inertial Effects in Electron Transfer Kinetics

Abstract

The electron transfer rates at the steady state are evaluated in terms of the Gaussian wave packet motion on free energy curves in the two-and three-surface models in the presence of inertial effects. The autocorrelation functions of the solvent polarization coordinate are fitted to the results of recent molecular dynamics simuJations. It is found that the inertial effects are particularly important for the electron transfer processes in acetontrile and water. They constitute an impeding factor in the wave packet motion. The neglect of the inertial part of the solvent autocorrelation function gives underestimation of the electron transfer rate coefficient.

Photoinduced Charge Separation Processes in Supramolecular Triad Systems

“…However, for a two-level system it has been shown that the inclusion of the reaction coordinate relaxation results in the line narrowing effect [60,61]. The central part of the line shape function is narrowed.…”