Symmetry or asymmetry of kET and iSTMvs. potential curves

R. A. Marcus

doi:10.1039/FT9969203905

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Journal of the Chemical Society, Faraday Transactions

Issue 20, 1996

Journal of the Chemical Society, Faraday Transactions; was published from 1990 - 1998. In 1999 it merged with a number of European chemical society physical Chemistry journals to become Physical Chemistry Chemical Physics.

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Symmetry or asymmetry of k_ET and i_STMvs. potential curves

R. A. Marcus

J. Chem. Soc., Faraday Trans., 1996,92, 3905-3908

DOI: 10.1039/FT9969203905

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Abstract
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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.

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Symmetry or asymmetry of kET and iSTMvs. potential curves

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Symmetry or asymmetry of k_ET and i_STMvs. potential curves