Understanding the response of the surface of metallic solids to external electric field sources is crucial to characterize electrode–electrolyte interfaces. Continuum electrostatics offer a simple description of the induced charge density at the electrode surface. However, such a simple description does not take into account features related to the atomic structure of the solid and to the molecular nature of the solvent and of the dissolved ions. In order to illustrate such effects and assess the ability of continuum electrostatics to describe the induced charge distribution, we investigate the behavior of a gold electrode interacting with sodium or chloride ions fixed at various positions, in a vacuum or in water, using all-atom constant-potential classical molecular dynamics simulations. Our analysis highlights important similarities between the two approaches, especially under vacuum conditions and when the ion is sufficiently far from the surface, as well as some limitations of the continuum description, namely, neglecting the charges induced by the adsorbed solvent molecules and the screening effect of the solvent when the ion is close to the surface. While the detailed features of the charge distribution are system-specific, we expect some of our generic conclusions on the induced charge density to hold for other ions, solvents, and electrode surfaces. Beyond this particular case, the present study also illustrates the relevance of such molecular simulations to serve as a reference for the design of improved implicit solvent models of electrode–electrolyte interfaces.
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A molecular perspective on induced charges on a metallic surface
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28 November 2021
Research Article|
November 30 2021
A molecular perspective on induced charges on a metallic surface
Special Collection:
The Chemical Physics of the Electrode-Electrolyte Interface
,
JCP Editors' Choice 2021
Giovanni Pireddu
;
Giovanni Pireddu
1
Sorbonne Université, CNRS, Physico-chimie des Électrolytes et Nanosystèmes Interfaciaux, PHENIX
, F-75005 Paris, France
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Laura Scalfi
;
Laura Scalfi
1
Sorbonne Université, CNRS, Physico-chimie des Électrolytes et Nanosystèmes Interfaciaux, PHENIX
, F-75005 Paris, France
2
Fachbereich Physik, Freie Universität Berlin
, 14195 Berlin, Germany
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Benjamin Rotenberg
Benjamin Rotenberg
a)
1
Sorbonne Université, CNRS, Physico-chimie des Électrolytes et Nanosystèmes Interfaciaux, PHENIX
, F-75005 Paris, France
3
Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459
, 80039 Amiens Cedex, France
a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on the Chemical Physics of the Electrode–Electrolyte Interface.
J. Chem. Phys. 155, 204705 (2021)
Article history
Received:
October 21 2021
Accepted:
November 05 2021
Citation
Giovanni Pireddu, Laura Scalfi, Benjamin Rotenberg; A molecular perspective on induced charges on a metallic surface. J. Chem. Phys. 28 November 2021; 155 (20): 204705. https://doi.org/10.1063/5.0076127
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