Marcus, R. A. (1996) Symmetry or asymmetry of k_(ET) and i_(STM) vs. potential curves. Journal of the Chemical Society. Faraday Transactions, 92 (20). pp. 3905-3908. ISSN 0956-5000 http://resolver.caltech.edu/CaltechAUTHORS:20120208-115452548
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The symmetry or asymmetry of STM current vs. bias potential and of electron transfer (ET) rate vs. overpotential curves is discussed for ET and for STM patterns across ordered monolayers. The superexchange expression for the electronic coupling matrix element, the Fermi–Dirac distribution and, for the ET reaction, the reorganization, are included. A mean potential approximation is assumed for the effect of bias or overpotential on the electronic orbitals or the ordered monolayer. Consequences for the symmetry vs. asymmetry of the ln(k_(ET))vs. overpotential and for the ln(i_(STM)) and pattern vs. bias are described. Examples of some relevant experiments are considered.
|Additional Information:||© 1996 Royal Society of Chemistry. Received 25th April, 1996.It is a pleasure to dedicate this article to Roger Parsons, whose clear article on electrified interfaces considerably facilitated my adapting to electrochemistry in 1957 some ideas that I had developed in the previous year for electron transfers in solution. I have acknowledged this special help in my Nobel address. It is a pleasure too, to acknowledge also the support of this research by the Office of Naval Research and the National Science Foundation.|
|Official Citation:||Symmetry or asymmetry of kET and iSTMvs. potential curves R. A. Marcus J. Chem. Soc., Faraday Trans., 1996, 92, 3905-3908 DOI: 10.1039/FT9969203905|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Ruth Sustaita|
|Deposited On:||08 Feb 2012 21:31|
|Last Modified:||26 Dec 2012 14:48|
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