The Relation Between the Barriers for Thermal and Optical Electron Transfer Reactions in Solution
Marcus, R. A. and Sutin, Norman (1986) The Relation Between the Barriers for Thermal and Optical Electron Transfer Reactions in Solution. Comments on Inorganic Chemistry, 5 (3). pp. 119-133. ISSN 0260-3594. http://resolver.caltech.edu/CaltechAUTHORS:20150630-112955684
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The relation between the energy of the intervalence (or metal-to-metal charge-transfer) transition in mixed-valence systems and the magnitude of the barrier to thermally activated electron transfer is described. We note that, contrary to what has frequently been assumed, the relation is in terms of free energies rather than internal energies or enthalpies. It is also shown, from plots of the enthalpies of the reactants and products versus the reaction coordinate, that negative activation enthalpies are a natural consequence when the standard enthalpy change for the reaction is sufficiently negative.
http://dx.doi.org/10.1080/02603598608072279 DOI Article
http://www.tandfonline.com/doi/abs/10.1080/02603598608072279 Publisher Article
© 1986 Gordon and Breach, Science Publishers, Inc. Published online: 13 Dec 2006. We wish to acknowledge helpful discussions with Drs. B. S. Brunschwig and C. Creutz. Research at Brookhaven National Laboratory (N.S.) was carried out under contract DE-AC02-76CH00016 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences. R. A. M. acknowledges support of his research by the Office of Naval Research; this is contribution No. 7280 from the Division of Chemistry and Chemical Engineering, California Institute of Technology.
Department of Energy (DOE) DE-AC02-76CH00016
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Caltech Division of Chemistry and Chemical Engineering 7280
The Relation Between the Barriers for Thermal and Optical Electron Transfer Reactions in Solution R. A. Marcus & Norman Sutin pages 119-133