Relationships between nonadiabatic bridged intramolecular, electrochemical, and electrical electron-transfer processes

Matthew C. Traub, Bruce S. Brunschwig, Nathan S Lewis

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)6676-6683
Number of pages8
JournalJournal of Physical Chemistry B
Volume111
Issue number24
DOIs
Publication statusPublished - Jun 21 2007

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electron transfer
Electrons
Gold
Electrodes
electrodes
Rate constants
Metals
gold
falling
metals
DNA
deoxyribonucleic acid
formulations
matrices
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Relationships between nonadiabatic bridged intramolecular, electrochemical, and electrical electron-transfer processes. / Traub, Matthew C.; Brunschwig, Bruce S.; Lewis, Nathan S.

In: Journal of Physical Chemistry B, Vol. 111, No. 24, 21.06.2007, p. 6676-6683.

Research output: Contribution to journalArticle

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