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Published 1996 | Published
Journal Article Open

Symmetry or asymmetry of k_(ET) and i_(STM) vs. potential curves

Abstract

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.

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August 20, 2023
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