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Relationships between Nonadiabatic Bridged Intramolecular, Electrochemical, and Electrical Electron-Transfer Processes

Traub, Matthew C. and Brunschwig, Bruce S. and Lewis, Nathan S. (2007) Relationships between Nonadiabatic Bridged Intramolecular, Electrochemical, and Electrical Electron-Transfer Processes. Journal of Physical Chemistry B, 111 (24). pp. 6676-6683. ISSN 1520-6106. doi:10.1021/jp065520g.

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Fermi's golden rule is used to develop relationships between rate constants for electron transfer in donor−bridge−acceptor and electrode−bridge−acceptor systems and resistances across metal−bridge−electrode and metal−bridge−tip junctions. Experimental data on electron-transfer rates through alkanethiolate, oligophenylene, and DNA bridges are used to calculate the electronic coupling matrix element per state through these moieties. The formulation is then used to predict the resistance of these bridges between two gold contacts. This approach provides a straightforward method for experimentalists to assess the self-consistency between intramolecular electron-transfer rate constants and low-bias resistances measured for molecularly bridged junctions between two metallic contacts. Reported resistances for alkanethiolate bridges vary by a factor of 20, with predicted resistances falling within this range. However, comparisons between carboxylato and directly linked alkanethiolate bridges suggest differences between the coupling at the interface to either the redox center or the gold electrode in such systems. Calculated resistances for oligophenylene bridges are close to those measured experimentally in a similar oligophenylene system.

Item Type:Article
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Brunschwig, Bruce S.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2007 American Chemical Society. Received: August 25, 2006; In Final Form: October 27, 2006. Publication Date (Web): April 12, 2007. We acknowledge the Department of Energy, Office of Basic Energy Sciences, and the Beckman Institute, for support of this work. We also acknowledge the extensive contributions and inspiration of Norman Sutin to the field of electron transfer which has provided the basis for this work. We specifically acknowledge the helpful comments Dr. Sutin provided on this manuscript.
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Department of Energy (DOE)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:24
Record Number:CaltechAUTHORS:20170426-111951613
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Official Citation:Relationships between Nonadiabatic Bridged Intramolecular, Electrochemical, and Electrical Electron-Transfer Processes Matthew C. Traub, Bruce S. Brunschwig, and Nathan S. Lewis The Journal of Physical Chemistry B 2007 111 (24), 6676-6683 DOI: 10.1021/jp065520g
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76950
Deposited By: Tony Diaz
Deposited On:26 Apr 2017 18:33
Last Modified:15 Nov 2021 17:04

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