Solvent reorganization energy of electron-transfer reactions in polar solvents.

A microscopic theory of solvent reorganization energy in polar molecular solvents is developed. The theory represents the solvent response as a combination of the density and polarization fluctuations of the solvent given in terms of the density and polarization structure factors. A fully analytical formulation of the theory is provided for a solute of arbitrary shape with an arbitrary distribution of charge. A good agreement between the analytical procedure and the results of Monte Carlo simulations of model systems is achieved. The reorganization energy splits into the contributions from density fluctuations and polarization fluctuations. The polarization part is dominated by longitudinal polarization response. The density part is inversely proportional to temperature. The dependence of the solvent reorganization energy on the solvent dipole moment and refractive index is discussed.