Electrochemistry in nanometer-wide electrochemical cells
The electrochemical properties of an electrochemical cell defined by two concentric spherical electrodes, separated by a 1 to 20-nm-wide gap, and a freely diffusing electrochemically active molecule (e.g., ferrocene) have been investigated by coupling of Brownian dynamics simulations with long-range...
| Publié dans: | Langmuir : the ACS journal of surfaces and colloids. - 1985. - 24(2008), 6 vom: 18. März, Seite 2850-5 |
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| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2008
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| Accès à la collection: | Langmuir : the ACS journal of surfaces and colloids |
| Sujets: | Journal Article |
| Résumé: | The electrochemical properties of an electrochemical cell defined by two concentric spherical electrodes, separated by a 1 to 20-nm-wide gap, and a freely diffusing electrochemically active molecule (e.g., ferrocene) have been investigated by coupling of Brownian dynamics simulations with long-range electron-transfer probability values. The simulation creates a trajectory of a single molecule and calculates the likelihood that the molecule undergoes a redox reaction during each time interval based on a probability-distance function derived from literature first-order kinetic data for a surface-bound ferrocene. Steady-state voltammograms for the single-molecule concentric spherical electrochemical cell are computed and are used to extract a heterogeneous electron-transfer rate for the freely diffusing molecule redox reaction. The Brownian dynamics simulations also indicate that long-range electron transfer, between the redox molecule and electrode, leads to nonsigmoidal-shaped i-E characteristics when the distance between electrodes approaches the characteristic redox tunneling decay length. The long-range electron transfer generates a "tunneling depletion layer" that results in a potential-dependent diffusion-limited current |
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| Description: | Date Completed 14.05.2008 Date Revised 11.03.2008 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1520-5827 |
| DOI: | 10.1021/la7031779 |