Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 118, Issue 29, Pages 15970-15977Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp5055843
Keywords
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Funding
- Swiss National Science Foundation
- RFBR [12-03-31748]
- FP7 project ACMOL [618082]
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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 In k(app) on barrier thickness in the range of ca. 6-20 angstrom 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.
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