Electron Transfer in Frozen Media.

Classical theories of electron transfer are modified to take into account the differences between electron transfer in a rigid medium and in a fluid. Intramolecular vibrations and part of the dielectric polarization are assumed to remain dynamic in rigid media while the remaining part of the polarization, arising from dipole reorientations, is frozen. In rigid media, electron transfer occurs with the solvent locked into the dipole orientations of the initial state. This causes an increase in the free energy change and a decrease in the solvent reorganizational energy. It also increases the activation free energy for electron transfer. For photoinduced electron transfer, the analysis is more complex because multiple states are involved. The activation free energy can either be greater or less than in a fluid depending on charge distributions before and after electron transfer. The same analysis can be applied to interconversion between excited states in rigid media.