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DPT modeling of Sta...
DPT modeling of Stark-Tuning effect : CO on polarized Pd(100) as a probe for double-layer electrostatic effects in electrochemistry
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- Bureau, C. (författare)
- CEA Saclay, France
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- Kranias, S. (författare)
- CEA Saclay, France
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- Crispin, Xavier (författare)
- University of Mons, Belgium
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visa fler...
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- Bredas, J. L. (författare)
- University of Mons, Belgium
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visa färre...
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(creator_code:org_t)
- Springer, 2000
- 2000
- Engelska.
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Ingår i: QUANTUM SYSTEMS IN CHEMISTRY AND PHYSICS, VOL 2. - : Springer. - 0792359704 ; , s. 169-192
- Relaterad länk:
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https://urn.kb.se/re...
Abstract
Ämnesord
Stäng
- The lifetime of chemisorbed radical anions produced in the electroreduction of vinylic molecules is thought to play a decisive part in the mechanism accounting for the production of grafted films in electropolymerization reactions. With the ultimate purpose of evaluating these lifetimes, we propose a one-dimensional model taking into account the interface bond, the anion/metallic surface image charge potential, and the anion/polarized-surface electrostatic repulsion. Orders of magnitude are known for the parameters entering in these terms, except for the latter. In the present work, this term is described using the Gouy-Chapmann model for the electrochemical double layer. Comparing our theoretical DFT predictions on Stark-Tuning effect of CO on Pd(100) with experiment, we can discuss on the legitimacy of a phenomenological linear relationship between the (microscopic) surface electric field and the (macroscopic) electrode potential. The slope of this relationship, termed the electric field rate, in (V.cm(-1)).V-1, turns out to be numerically equivalent to the characteristic length of the double layer, whatever the underlying model. Our calculated rates, carried out within the Gouy-Chapmann approximation, are in acceptable agreement with previous experimental estimates. First insights into our electropolymerization reactions suggest that the presumed intermediate chemisorbed radical-anions may have a borderline stability, i.e. a largely non negligible lifetime on the surface.
Nyckelord
- DENSITY-FUNCTIONAL THEORY; CARBON-MONOXIDE; PLATINUM-ELECTRODE; METAL-SURFACES; INFRARED-SPECTRUM; BASIS-SETS; SPECTROSCOPY; ADSORPTION; APPROXIMATION; ACRYLONITRILE
- TECHNOLOGY
- TEKNIKVETENSKAP
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