MetalWalls

Author(s)
Alessandro Coretti, Camille Bacon, Roxanne Berthin, Alessandra Serva, Laura Scalfi, Iurii Chubak, Kateryna Goloviznina, Matthieu Haefele, Abel Marin-Lafleche, Benjamin Rotenberg, Sara Bonella, Mathieu Salanne
Abstract

Electrochemistry is central to many applications, ranging from biology to energy science. Studies now involve a wide range of techniques, both experimental and theoretical. Modeling and simulations methods, such as density functional theory or molecular dynamics, provide key information on the structural and dynamic properties of the systems. Of particular importance are polarization effects of the electrode/electrolyte interface, which are difficult to simulate accurately. Here, we show how these electrostatic interactions are taken into account in the framework of the Ewald summation method. We discuss, in particular, the formal setup for calculations that enforce periodic boundary conditions in two directions, a geometry that more closely reflects the characteristics of typical electrolyte/electrode systems and presents some differences with respect to the more common case of periodic boundary conditions in three dimensions. These formal developments are implemented and tested in MetalWalls, a molecular dynamics software that captures the polarization of the electrolyte and allows the simulation of electrodes maintained at a constant potential. We also discuss the technical aspects involved in the calculation of two sets of coupled degrees of freedom, namely the induced dipoles and the electrode charges. We validate the implementation, first on simple systems, then on the well-known interface between graphite electrodes and a room-temperature ionic liquid. We finally illustrate the capabilities of MetalWalls by studying the adsorption of a complex functionalized electrolyte on a graphite electrode.

Organisation(s)
Computational and Soft Matter Physics
External organisation(s)
Politecnico di Torino, École polytechnique fédérale de Lausanne, Centre National De La Recherche Scientifique (CNRS), Sorbonne Université, Université de Pau et des Pays de l'Adour, Université Paris Saclay, Institut Universitaire de France, Paris 75005, France.
Journal
Journal of Chemical Physics
Volume
157
No. of pages
15
ISSN
0021-9606
DOI
https://doi.org/10.1063/5.0101777
Publication date
11-2022
Peer reviewed
Yes
Austrian Fields of Science 2012
104005 Electrochemistry, 103006 Chemical physics
Keywords
ASJC Scopus subject areas
General Physics and Astronomy, Physical and Theoretical Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/a4ead743-33d5-4b8a-84fe-01b562d7be88