Simulating Electrochemical Systems by Combining the Finite Field Method with a Constant Potential Electrode

Thomas Dufils, Guillaume Jeanmairet, Benjamin Rotenberg, Michiel Sprik, and Mathieu Salanne
Phys. Rev. Lett. 123, 195501 – Published 4 November 2019
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Abstract

A better understanding of interfacial mechanisms is needed to improve the performances of electrochemical devices. Yet, simulating an electrode surface at fixed electrolyte composition remains a challenge. Here, we apply a finite electric field to a single electrode held at constant potential and in contact with an aqueous ionic solution, using classical molecular dynamics. The polarization yields two electrochemical interfaces on opposite sides of the same metal slab. The net charge on one electrode surface is the opposite of the net charge on the other, maintaining overall charge neutrality of the metal. The electrode surface charge fluctuations are compensated by the adsorption of ions from the electrolyte, forming a pair of electric double layers with aligned dipoles. This opens the way towards the efficient simulation of electrochemical interfaces using any flavor of molecular dynamics, from classical to first-principles-based methods.

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  • Received 2 July 2019

DOI:https://doi.org/10.1103/PhysRevLett.123.195501

© 2019 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied PhysicsStatistical Physics & Thermodynamics

Authors & Affiliations

Thomas Dufils1, Guillaume Jeanmairet1, Benjamin Rotenberg1, Michiel Sprik2, and Mathieu Salanne1,*

  • 1Sorbonne Université, CNRS, Physico-chimie des Électrolytes et Nanosystèmes Interfaciaux, PHENIX, F-75005 Paris, France
  • 2Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom

  • *Corresponding author. mathieu.salanne@sorbonne-universite.fr

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Issue

Vol. 123, Iss. 19 — 8 November 2019

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