Reorganization Free Energy for Electron Transfers at Liquid-Liquid and DielectricSemiconductor-Liquid Interfaces

摘要

The reorganization free energy is calculated for a reaction between (i) tworeactants, 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. The reorganization energy for a semiconductor/liquid system can differ considerably from the corresponding metal/liquid value, even a factor of two. (jes)