Unusual Distance Dependences of Electron Transfer Rates

Kuss-Petermann, Martin and Wenger, Oliver S.. (2016) Unusual Distance Dependences of Electron Transfer Rates. Physical Chemistry Chemical Physics, 18 (28). pp. 18657-18664.

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Usually the rates for electron transfer (kET) decrease with increasing donor–acceptor distance, but Marcus theory predicts a regime in which kET is expected to increase when the transfer distance gets longer. Until recently, experimental evidence for such counter-intuitive behavior had been very limited, and consequently this effect is much less well-known than the Gaussian free energy dependence of electron transfer rates leading to the so-called inverted driving-force effect. This article presents the theoretical concepts that lead to the prediction of electron transfer rate maxima at large donor–acceptor distances, and it discusses conditions that are expected to favor experimental observations of such behavior. It continues with a consideration of specific recent examples in which electron transfer rates were observed to increase with increasing donor–acceptor distance, and it closes with a discussion of the importance of this effect in the context of light-to-chemical energy conversion.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Kuss-Petermann, Martin
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
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edoc DOI:
Last Modified:11 Jan 2017 14:55
Deposited On:11 Jan 2017 14:53

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