Charge Separation Reaction in Clusters of Polar Molecules: MD Simulations

Rate constant of intermolecular electron transfer (ET) in a photoexcited donor/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 constant have been compared with the corresponding MD results for the donor/acceptor pair solvated in bulk acetonitrile, and with theoretical predictions based on the continuum model.