Long Distance Electron Transfer at the Metal/Alkanethiol/Ionic Liquid Interface

Nikitina, Victoria A.; Rudnev, Alexander; Tsirlina, Galina A.; Wandlowski, Thomas (2014). Long Distance Electron Transfer at the Metal/Alkanethiol/Ionic Liquid Interface. Journal of physical chemistry. C, 118(29), pp. 15970-15977. American Chemical Society 10.1021/jp5055843

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The rate constants of simple electron transfer (ET) reactions in room temperature ionic liquids (ILs) available now are rather high, typically at the edge of experimental accuracy. To consider ET phenomena in these media in view of theory developed earlier for molecular solvents, it is crucial to provide quantitative comparison of experimental kinetic data for certain reactions. We report this comparison for ferrocene/ferrocenium reaction. The ET distance is fixed by Au surface modification by alkanethiol self-assembled monolayers, which were characterized by in situ scanning tunneling microscopy. The dependence of ln kapp on barrier thickness in the range of ca. 6–20 Å is linear, with a slope typical for the same plots in aqueous media. This result confirms diabatic mode of Fc oxidation at long distance. The data for shorter ET distances point to the adiabatic regime of ET at a bare gold surface, although more detailed computational studies are required to justify this conclusion.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Rudnev, Alexander and Wandlowski, Thomas

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
500 Science

ISSN:

1932-7447

Publisher:

American Chemical Society

Language:

English

Submitter:

Beatrice Niederhauser

Date Deposited:

26 Mar 2015 10:47

Last Modified:

25 Aug 2015 10:26

Publisher DOI:

10.1021/jp5055843

BORIS DOI:

10.7892/boris.65946

URI:

https://boris.unibe.ch/id/eprint/65946

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