The free energy gap and temperature dependence of the electronic transmission coefficient in electron-transfer reactions of the solvated electron

We have investigated the dependence of the electronic factor in electron-transfer rate constants on the energy gap and temperature by minimizing the electronic energy with respect to the instantaneous non-equilibrium solvent polarization. The electronic charge billows out and shrinks in the “normal” and strongly exothermic free energy region, respectively, but the effect is only comparable to the variation of the nuclear factor for low temperatures and strongly exothermic processes.