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Implications of an Electron-Hopping Model for Charge Transport through Donor−Bridge−Acceptor Assemblies Connected to Metal Electrodes

Sutin, Norman and Brunschwig, Bruce S. and Creutz, Carol and Feldberg, Stephen W. (2004) Implications of an Electron-Hopping Model for Charge Transport through Donor−Bridge−Acceptor Assemblies Connected to Metal Electrodes. Journal of Physical Chemistry B, 108 (32). pp. 12092-12102. ISSN 1520-6106. doi:10.1021/jp048133k. https://resolver.caltech.edu/CaltechAUTHORS:20170524-141116151

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Abstract

An electron-hopping model for electrode-to-electrode charge transport through donor-bridge-acceptor assemblies (J. Phys. Chem. B 2003, 107, 10687) is further developed by detailed electrostatic analysis of the assembly and treatment of the steady-state kinetics. Charge transport between the two electrodes proceeds via the D−B−A bridges:  D transfers an electron to A through the bridge. The newly formed D+ and A- are then rapidly reduced and oxidized, respectively, at the electrodes giving rise to a steady state in which the current depends on the rate of electron transfer from D to A. The driving force dependence of the nuclear factor for the D to A electron transfer results in the current through the D−B−A bridge increasing with applied voltage (positive differential conductance) in the normal free-energy region but decreasing in the inverted region (negative differential conductance). The electronic factors can be manipulated by changing the separations between the electrodes and DBA or the length of B or by changing the nature of the bridge material. Decreasing the electronic factor for D to A electron transfer decreases the flux at a given applied voltage in the normal region, but the effect is much greater in the inverted region. Possible parallel tunneling and electron hopping mechanisms that could contribute to the current and interfere with the region of negative differential resistance are analyzed in detail. For the coupled electron-transfer sequence considered here, changing electronic factors result in dramatic shifts of the reaction profile.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp048133kDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp048133kPublisherArticle
ORCID:
AuthorORCID
Brunschwig, Bruce S.0000-0002-6135-6727
Additional Information:© 2004 American Chemical Society. Received 29 April 2004. Published online 16 July 2004. Published in print 1 August 2004. This research was carried out at Brookhaven National Laboratory under contract DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences. Note Added after ASAP Posting. A variable in eq 58 was changed from that which was originally published on 7/16/2004. The correct version was posted on 7/28/2004.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-98CH10886
Issue or Number:32
DOI:10.1021/jp048133k
Record Number:CaltechAUTHORS:20170524-141116151
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170524-141116151
Official Citation:Implications of an Electron-Hopping Model for Charge Transport through Donor−Bridge−Acceptor Assemblies Connected to Metal Electrodes Norman Sutin, Bruce S. Brunschwig, Carol Creutz, and Stephen W. Feldberg The Journal of Physical Chemistry B 2004 108 (32), 12092-12102 DOI: 10.1021/jp048133k
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77723
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:24 May 2017 21:38
Last Modified:15 Nov 2021 17:33

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