Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 4528-4532 |
| Number of pages | 5 |
| Journal | Proceedings of the National Academy of Sciences of the United States of America |
| Volume | 107 |
| Issue number | 10 |
| DOIs | |
| State | Published - 9 Mar 2010 |
Keywords
- Butler-Volmer kinetics
- Chemical master equation
- Electrochemistry
- Electrode kinetics
- Nanoelectrodes