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Issue 28, 2016
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Unusual distance dependences of electron transfer rates

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Abstract

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.

Graphical abstract: Unusual distance dependences of electron transfer rates

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Article information


Submitted
09 May 2016
Accepted
15 Jun 2016
First published
29 Jun 2016

This article is Open Access

Phys. Chem. Chem. Phys., 2016,18, 18657-18664
Article type
Perspective

Unusual distance dependences of electron transfer rates

M. Kuss-Petermann and O. S. Wenger, Phys. Chem. Chem. Phys., 2016, 18, 18657
DOI: 10.1039/C6CP03124B

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