A Kramers reaction rate theory for electrochemical ion transfer reactions

Autor:	Wolfgang Schmickler, Marc T.M. Koper
Rok vydání:	1996
Předmět:	Reaction rate Partial charge Adsorption Reaction rate constant Chemistry Charge transfer coefficient Analytical chemistry General Physics and Astronomy Thermodynamics Physical and Theoretical Chemistry Adiabatic process Electrochemistry Reaction coordinate
Zdroj:	Chemical Physics. 211:123-133
ISSN:	0301-0104
DOI:	10.1016/0301-0104(96)00248-0
Popis:	A simple model for electrochemical ion transfer reactions, based on an extended Anderson-Newns model [W. Schmickler, Chem. Phys. Lett. 237 (1995) 152], is treated within the framework of the multidimensional Kramers theory to calculate ion transfer rates. It is shown that for univalent ion transfer, the rate constant may be substantially influenced by a partial charge transfer during the rate-determining step of the adsorption process, even though the activation barrier is mainly determined by the separation from the metal surface. In the limit of strongly overdamped solvent dynamics, however, the energetically favourable adiabatic electron exchange with the electrode is suppressed and the effective reaction coordinate is again one-dimensional, and given by the separation from the surface.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::d9c2e1d3c10141bb7994860fa93d5f04 https://doi.org/10.1016/0301-0104(96)00248-0 Zobrazit plný text záznamu Full Text from ScienceDirect