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Theories of electrode kinetics

Marcus, R. A. (1977) Theories of electrode kinetics. In: Proceedings of the Conference on Physicochemical Hydrodynamics. Vol.1. Advance Publications Ltd. , London, pp. 473-482. ISBN 0-903012-40-5.

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The present lecture consists of two parts. In the first, a comparison is made of theory and experiment for simple electron transfer reactions in solution and at electrodes, reactions for which no bonds are broken of formed. The main part of the lecture is concerned with electrode reactions involving the breaking and forming of chemical bonds and principally with the hydronium ion discharge reaction, H_3O(+) + M(e) yields H_2O + H-M(ads.). The treatment of this reaction has been the subject of some controversy (cf. 1965 Faraday Discussions on Proton Transfer and more recent literature). To provide further insight, a more dynamical theory of this elementary step for general potential energy surfaces is described. It is then shown how, depending on the nature of the potential energy surface, the theory leads to various approaches in the literature. For example, depending on the surface, the system may or may not for dynamical reasons be able to reach sufficiently easily the saddle-point region or, again, Franck-Condon solvation effects may or may not contribute to the rate. There is a clear need for the application of recent theoretical methods of electronic structure to determine the essential features of the potential energy surface.

Item Type:Book Section
Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1977. It is a pleasure to acknowledge the support of this research by the Office of Naval Research.
Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
Subject Keywords:Electrodes, Electron Transfer, Protons, Reaction Kinetics, Electron Transitions, Ions, Metals, Potential Energy, Surface Reactions
Record Number:CaltechAUTHORS:20150928-124501792
Persistent URL:
Official Citation:Theories of Electrode Kinetics R. A. Marcus Physicochem. Hydrodyn. (Pap. Conf.) 1, 473 (1977)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60577
Deposited On:30 Sep 2015 21:48
Last Modified:22 Nov 2019 09:58

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