Theory of electron-transfer processes via chemisorbed intermediates

Mishra, A. K. ; Rangarajan, S. K. (1987) Theory of electron-transfer processes via chemisorbed intermediates Journal of Physical Chemistry, 91 (12). pp. 3417-3425. ISSN 0022-3654

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Official URL: http://pubs.acs.org/doi/abs/10.1021/j100296a062

Related URL: http://dx.doi.org/10.1021/j100296a062

Abstract

A model Hamiltonian to describe adsorbate-mediated electron transfer is proposed and analyzed for the (electrochem.) currents. This Hamiltonian differs fundamentally from the ones used earlier (cf. Schmickler 1980, 1982). Three situations are treated, viz., (1) a lone adsorbate picture; (2) presence of an inactive neighboring adsorbate; and (3) electrostatic effects due to an adsorbate lattice. In all 3 cases, the mediation is via a single adsorbate only. Several limiting cases are considered and related to the earlier results of Marcus and Schmickler.

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