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Long-Range Electron Tunneling

Winkler, Jay R. and Gray, Harry B. (2014) Long-Range Electron Tunneling. Journal of the American Chemical Society, 136 (8). pp. 2930-2939. ISSN 0002-7863. PMCID PMC3986022 . doi:10.1021/ja500215j.

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Electrons have so little mass that in less than a second they can tunnel through potential energy barriers that are several electron-volts high and several nanometers wide. Electron tunneling is a critical functional element in a broad spectrum of applications, ranging from semiconductor diodes to the photosynthetic and respiratory charge transport chains. Prior to the 1970s, chemists generally believed that reactants had to collide in order to effect a transformation. Experimental demonstrations that electrons can transfer between reactants separated by several nanometers led to a revision of the chemical reaction paradigm. Experimental investigations of electron exchange between redox partners separated by molecular bridges have elucidated many fundamental properties of these reactions, particularly the variation of rate constants with distance. Theoretical work has provided critical insights into the superexchange mechanism of electronic coupling between distant redox centers. Kinetics measurements have shown that electrons can tunnel about 2.5 nm through proteins on biologically relevant time scales. Longer-distance biological charge flow requires multiple electron tunneling steps through chains of redox cofactors. The range of phenomena that depends on long-range electron tunneling continues to expand, providing new challenges for both theory and experiment.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Published In Issue: February 26, 2014. Article ASAP: February 18, 2014. Just Accepted Manuscript: February 05, 2014. Received: January 08, 2014. Our electron transfer research is supported by the National Institutes of Health (DK-019038), the National Science Foundation (CHE-1305124), the Gordon and Betty Moore Foundation, and the Arnold and Mabel Beckman Foundation. Supporting Information: Estimation of the gas-phase Fc+/Fc electron exchange tunneling energy and additional comparisons of amino acid occurrence frequencies. This material is available free of charge via the Internet at
Group:CCI Solar Fuels
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:8
PubMed Central ID:PMC3986022
Record Number:CaltechAUTHORS:20140403-144433692
Persistent URL:
Official Citation:Long-Range Electron Tunneling Jay R. Winkler and Harry B. Gray Journal of the American Chemical Society 2014 136 (8), 2930-2939
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:44645
Deposited By: George Porter
Deposited On:03 Apr 2014 21:53
Last Modified:10 Nov 2021 16:54

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