Solvent nuclear quantum effects in electron transfer reactions II. Molecular dynamics study on methanol solution

Solvent nuclear quantum effects in outer-sphere electron transfer (ET) reactions in methanol solution are examined via a molecular dynamics simulation analysis. The energy gap law of the quantum mechanical ET rate constant is decomposed into contributions from solvent intramolecular vibrations and other low-frequency intermolecular (collective) modes. It is shown that the high-frequency stretching and bending vibrations from the hydroxyl part of the solvent methanol exhibit marked quantum effects on the ET rate despite of their fractional contributions to the reorganization energy (computed to be