Note to users. If you're seeing this message, it means that your browser cannot find this page's style/presentation instructions -- or possibly that you are using a browser that does not support current Web standards. Find out more about why this message is appearing, and what you can do to make your experience of our site the best it can be.

Science 22 February 1991:
Vol. 251. no. 4996, pp. 919 - 922
DOI: 10.1126/science.251.4996.919
Prev | Table of Contents | Next

Articles

Free Energy and Temperature Dependence of Electron Transfer at the Metal-Electrolyte Interface

CHRISTOPHER E. D. CHIDSEY 1

1 AT&T Bell Laboratories, Murray Hill, NJ 07974

The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1° to 47°C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eegr5C5H5)Fe(eegr5C5H4)CO2(CH2)16SH and CH3(CH2)15SH. Rate constants from 1 per second (s–1) to 2 x 104 s–1 in 1 molar HClO4 are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 104 s–1 eV–1. Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions.

Submitted on August 30, 1990
Accepted on November 12, 1990


THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
The study of charge transport through organic thin films: mechanism, tools and applications.
E. A Weiss, J. K Kriebel, M.-A. Rampi, and G. M Whitesides (2007)
Phil Trans R Soc A 365, 1509-1537
   Abstract »    Full Text »    PDF »
A Cytochrome c Oxidase Model Catalyzes Oxygen to Water Reduction Under Rate-Limiting Electron Flux.
J. P. Collman, N. K. Devaraj, R. A. Decreau, Y. Yang, Y.-L. Yan, W. Ebina, T. A. Eberspacher, and C. E. D. Chidsey (2007)
Science 315, 1565-1568
   Abstract »    Full Text »    PDF »
Measurement of Single-Molecule Resistance by Repeated Formation of Molecular Junctions.
B. Xu and N. J. Tao (2003)
Science 301, 1221-1223
   Abstract »    Full Text »    PDF »
Surface-Driven Switching of Liquid Crystals Using Redox-Active Groups on Electrodes.
Y.-Y. Luk and N. L. Abbott (2003)
Science 301, 623-626
   Abstract »    Full Text »    PDF »
Supramolecular Chemistry And Self-assembly Special Feature: Metal ion recognition and molecular templating in self-assembled monolayers of cyclic and acyclic polyethers.
M. A. Herranz, B. Colonna, and L. Echegoyen (2002)
PNAS 99, 5040-5047
   Abstract »    Full Text »    PDF »
The Dependence of Electron Transfer Efficiency on the Conformational Order in Organic Monolayers.
A. Haran, D. H. Waldeck, R. Naaman, E. Moons, and D. Cahen (1994)
Science 263, 948-950
   Abstract »    PDF »


To Advertise     Find Products

Science. ISSN 0036-8075 (print), 1095-9203 (online)