| A microscopic theory is developed to study the dynamic and energetic solvent effects on charge transfer (CT) reactions in molecular fluids. The theory is based on a simple renormalized linear response development which incorporates the nonlinear aspects of equilibrium solvation. In combination with the Reference Memory Function Approximation (RMFA) for the evaluation of time correlation functions of a certain solvent density field, the theory is able to capture the non-Markovian dynamical informations in the complex many-body interacting systems. We apply a dielectric version of the theory to study the solvation time correlation function ;An important feafure of the theory is that it is formulated for general interaction site models (ISM) of molecules, hence both the solute and the solvent can have quite realistic molecular "size", "shape", and mutual interactions. Furthermore, we generalize the theory to accommodate polarizable solvent molecules as well as the limiting case represented by electronically rigid interaction site model solvent molecules. By studying CT processes in ISM solution models we naturally cover both the short range and long range solute-solvent interactions, thereby enabling applications to CT in solvents of higher multipolar as well as dipolar character. As an example, with a simple four-site ISM model of betaine-30 dye, the theory correctly predicts the ordering and the magnitude of the measured solvent contribution to the vertical energy transition of betaine-30 for a selection of nine solvents covering a wide range of polarity. |
