Reorganization free energy for electron transfers at liquid-liquid and dielectric semiconductor-liquid interfaces

The reorganization free energy is calculated for a reaction (i) between two reactants, each in its own dielectric medium, separated by an interface, and (ii) between a reactant and some semiconductors. An expression is also given for the rate constant of an electron-transfer reaction at an interface between reactants in two immiscible phases. Under certain conditions it is shown that the reorganization energy for the two immiscible-liquid system is the sum of the electrochemical reorganization energies of the two reactants, each in its own respective solvent. The reorganization energy for a semiconductor-liquid system can differ considerably from the corresponding metal-liquid value, even a factor of 2