Charge separation reaction in clusters of polar molecules: MD simulations

Abstract

Rate constaaat of intermolecular electron transfer (ET) in a photoexcited dono~acceptor model system solvated by a cluster of polar molecules has been expressed in terms of the statistical distribution of the electrostatic potential energy difference between the reacting sites. This distribution has been calculated for a particular case of acetonitrile clusters at ~-120 K by MD computer simulation. The MD values of the cluster reorganization energy and the ET rate constaaat have been compared with the corresponding MD results for the dono~acceptor pair solvated in bulk acetonitrile and with theoretical predictions based on the continuum model.

Influence of distortion and Duschinsky effects on Marcus-type theories of electron transfer rate

“…It is very challenging to study the contribution of the surroundings either for intermolecular or intramolecular ET processes. [12][13][14][15][16][17][18][19][20] Comparatively, the parameters defining the PES in the intramolecular normal vibrational coordinates could be more easily obtained. For example, analysis of continuouswave (CW) spectra of the molecules or quantum-chemical calculations could provide useful information on the structure of the PESs.…”