Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 107, Issue 10, Pages 4528-4532Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0909240107
Keywords
Butler-Volmer kinetics; chemical master equation; electrochemistry; electrode kinetics; nanoelectrodes
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Funding
- European Union [028669]
- cluster of excellence Nanosystems Initiative Munich (NIM)
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The electrode potential constitutes a dynamical variable whenever an electrode is resistively coupled to the electric circuit. We show that at the nanoscale, the discreteness and stochasticity of an electron transfer event causes fluctuations of the electrode potential that render all elementary electrochemical reactions to be faster on a nanoelectrode than predicted by the macroscopic (Butler Volmer) electrochemical kinetics. This phenomenon is substantiated by means of a generalized (electro) chemical master equation.
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