Reorganization of Intramolecular High Frequency Vibrational Modes and Dynamic Solvent Effect in Electron Transfer Reactions

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 116; no. 16; pp. 4010 - 4019
• Main Authors: Yudanov, Vladislav V, Mikhailova, Valentina A, Ivanov, Anatoly I
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 26.04.2012
• Subjects: Dynamics; Electron transfer; High frequencies; Mathematical models; Multichannel; Rate constants; Solvents; Stochasticity
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp301837t

The possibility of the multichannel stochastic model to adequately describe all principal regularities observed in thermal electron transfer kinetics has been demonstrated. The most important are as follows: (i) the model predicts the solvent controlled regime in the Marcus normal region and its almost full suppression in the Marcus inverted region as well as a continuous transition between them in the vicinity of the activationless region; (ii) the suppression of dynamic solvent effect (DSE) is principally caused by the reorganization of high frequency vibrational modes; (iii) an additional factor of the DSE suppression stems from fast solvent relaxation component; (iv) in the inverted region, the multichannel stochastic model predicts the apparent activation energy to be much less than that calculated with Marcus equation. The exploration of the multichannel stochastic model has allowed one to conclude that the reorganization of high frequency vibrational modes can (i) raise the maximum rate constant above the solvent controlled limit by 2 and more orders of magnitude, (ii) shift the rate constant maximum to larger values of the free energy gap, and (iii) approach the electron transfer kinetics to the nonadiabatic regime.