The effect of intramolecular quantum modes on free energy relationships for electron transfer reactions

TLDR: In this article, a general quantum description of exothermic electron transfer reactions is formulated by treating such reactions as the nonradiative decay of a "supermolecule" consisting of the electron donor, the electron acceptor, and the polar solvent.

Abstract: A general quantum mechanical description of exothermic electron transfer reactions is formulated by treating such reactions as the nonradiative decay of a ’’supermolecule’’ consisting of the electron donor, the electron acceptor, and the polar solvent. In particular, the role of the high‐frequency intramolecular degrees of feedom on the free energy relationship for series of closely related reactions was investigated for various model systems involving displacement of potential energy surfaces, frequency shift, and anharmonicity effects. The free energy plots are generally found to pass through a maximum and to be asymmetric with a slower decrease in the transition probability with increasing energy of reaction. For high‐frequency intramolecular modes this provides a rationalization of the experimental observation of ’’activationless’’ regions. Isotope effects are discussed as also are the oscillatory free energy relationships, predicted for low temperatures and high frequencies, and which are analogous t...

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The effect of intramolecular quantum modes on free energy relationships for electron
transfer reactions
Ulstrup, Jens; Jortner, Joshua
Published in:
Journal of Chemical Physics
Link to article, DOI:
10.1063/1.431152
Publication date:
1975
Document Version
Publisher's PDF, also known as Version of record
Link back to DTU Orbit
Citation (APA):
Ulstrup, J., & Jortner, J. (1975). The effect of intramolecular quantum modes on free energy relationships for
electron transfer reactions. Journal of Chemical Physics, 63(10), 4358-4368. https://doi.org/10.1063/1.431152

Downloaded 25 Aug 2009 to 192.38.67.112. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/jcp/copyright.jsp

Downloaded 25 Aug 2009 to 192.38.67.112. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/jcp/copyright.jsp

Downloaded 25 Aug 2009 to 192.38.67.112. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/jcp/copyright.jsp

Downloaded 25 Aug 2009 to 192.38.67.112. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/jcp/copyright.jsp

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