Continuum electrolyte models represent a practical tool to account for the presence of the diffuse layer at electrochemical interfaces. However, despite the increasing popularity of these in the field of materials science, it remains unclear which features are necessary in order to accurately describe interface-related observables such as the differential capacitance (DC) of metal electrode surfaces. We present here a critical comparison of continuum diffuse-layer models that can be coupled to an atomistic first-principles description of the charged metal surface in order to account for the electrolyte screening at electrified interfaces. By comparing computed DC values for the prototypical Ag(100) surface in an aqueous solution to experimental data, we validate the accuracy of the models considered. Results suggest that a size-modified Poisson-Boltzmann description of the electrolyte solution is sufficient to qualitatively reproduce the main experimental trends. Our findings also highlight the large effect that the dielectric cavity parameterization has on the computed DC values.
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28 January 2019
Research Article|
December 26 2018
Continuum models of the electrochemical diffuse layer in electronic-structure calculations
Special Collection:
Interfacial Electrochemistry and Photo(electro)catalysis
,
JCP Editors' Choice 2018
Francesco Nattino
;
Francesco Nattino
1
Theory and Simulations of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne
, CH-1015 Lausanne, Switzerland
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Matthew Truscott
;
Matthew Truscott
2
Department of Physics, University of North Texas
, Denton, Texas 76207, USA
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Nicola Marzari
;
Nicola Marzari
1
Theory and Simulations of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne
, CH-1015 Lausanne, Switzerland
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Oliviero Andreussi
Oliviero Andreussi
2
Department of Physics, University of North Texas
, Denton, Texas 76207, USA
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Francesco Nattino
1
Matthew Truscott
2
Nicola Marzari
1
Oliviero Andreussi
2
1
Theory and Simulations of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne
, CH-1015 Lausanne, Switzerland
2
Department of Physics, University of North Texas
, Denton, Texas 76207, USA
J. Chem. Phys. 150, 041722 (2019)
Article history
Received:
August 31 2018
Accepted:
November 07 2018
Citation
Francesco Nattino, Matthew Truscott, Nicola Marzari, Oliviero Andreussi; Continuum models of the electrochemical diffuse layer in electronic-structure calculations. J. Chem. Phys. 28 January 2019; 150 (4): 041722. https://doi.org/10.1063/1.5054588
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