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

Creators: Marcus, R. A.

Abstract

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.

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© 1990 American Chemical Society. Received: July 7, 1989. It is a pleasure to participate in this issue honoring Harry Drickamer, a long-time friend and colleague at Illinois. Somehow, with his love of history, it seemed appropriate to return to a subject initiated some years ago, and perhaps in his many contributions he has occasionally done the same. Acknowledgment is made to the Office of Naval Research and to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for the support of this research. I thank B. B. Smith, C. A. Koval, and N. Lewis and his students for calling my attention to some of these problems and for useful discussions.

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

Abstract

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