The single-molecule conductance and electrochemical electron-transfer rate are related by a power law.

Published

Journal Article

This study examines quantitative correlations between molecular conductances and standard electrochemical rate constants for alkanes and peptide nucleic acid (PNA) oligomers as a function of the length, structure, and charge transport mechanism. The experimental data show a power-law relationship between conductances and charge transfer rates within a given class of molecules with the same bridge chemistry, and a lack of correlation when a more diverse group of molecules is compared, in contrast with some theoretical predictions. Surprisingly, the PNA duplexes exhibit the lowest charge-transfer rates and the highest molecular conductances. The nonlinear rate-conductance relationships for structures with the same bridging chemistries are attributed to differences in the charge-mediation characteristics of the molecular bridge, energy barrier shifts and electronic dephasing, in the two different experimental settings.

Full Text

Duke Authors

Cited Authors

  • Wierzbinski, E; Venkatramani, R; Davis, KL; Bezer, S; Kong, J; Xing, Y; Borguet, E; Achim, C; Beratan, DN; Waldeck, DH

Published Date

  • June 2013

Published In

Volume / Issue

  • 7 / 6

Start / End Page

  • 5391 - 5401

PubMed ID

  • 23692478

Pubmed Central ID

  • 23692478

Electronic International Standard Serial Number (EISSN)

  • 1936-086X

International Standard Serial Number (ISSN)

  • 1936-0851

Digital Object Identifier (DOI)

  • 10.1021/nn401321k

Language

  • eng