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Title: | Constant chemical potential-quantum mechanical-molecular dynamics simulations of the graphene-electrolyte double layer |
Authors: | Di Pasquale, N Finney, AR Elliott, JD Carbone, P Salvalaglio, M |
Keywords: | classical force fields;molecular dynamics;quantum mechanical calculations;cluster dynamics;electrolytes;interfaces;electrical double layers |
Issue Date: | 4-Apr-2023 |
Publisher: | AIP Publishing |
Citation: | Di Pasquale, N. et al. (2023) 'Constant chemical potential-quantum mechanical-molecular dynamics simulations of the graphene-electrolyte double layer', Journal of Chemical Physics, 158 (13), 134714, pp. 1 - 15. doi: 10.1063/5.0138267. |
Abstract: | We present the coupling of two frameworks—the pseudo-open boundary simulation method known as constant potential molecular dynamics simulations (CμMD), combined with quantum mechanics/molecular dynamics (QMMD) calculations—to describe the properties of graphene electrodes in contact with electrolytes. The resulting CμQMMD model was then applied to three ionic solutions (LiCl, NaCl, and KCl in water) at bulk solution concentrations ranging from 0.5 M to 6 M in contact with a charged graphene electrode. The new approach we are describing here provides a simulation protocol to control the concentration of electrolyte solutions while including the effects of a fully polarizable electrode surface. Thanks to this coupling, we are able to accurately model both the electrode and solution side of the double layer and provide a thorough analysis of the properties of electrolytes at charged interfaces, such as the screening ability of the electrolyte and the electrostatic potential profile. We also report the calculation of the integral electrochemical double layer capacitance in the whole range of concentrations analyzed for each ionic species, while the quantum mechanical simulations provide access to the differential and integral quantum capacitance. We highlight how subtle features, such as the adsorption of potassium graphene or the tendency of the ions to form clusters contribute to the ability of graphene to store charge, and suggest implications for desalination |
Description: | Supplementary data are available online at https://pubs.aip.org/jcp/article-supplement/2883280/zip/134714_1_5.0138267.suppl_material/ . A preprint version of this article is available at arXiv:2212.03990v2 [cond-mat.mtrl-sci] , https://arxiv.org/abs/2212.03990v2 under a Creative Commons (CC BY) Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/). It has not been certified by peer review. Please refer to the published version available at https://doi.org/10.1063/5.0138267, also archived on this institutional repository. |
URI: | https://bura.brunel.ac.uk/handle/2438/26551 |
DOI: | https://doi.org/10.1063/5.0138267 |
ISSN: | 0021-9606 |
Other Identifiers: | ORCiD: Nicodemo Di Pasquale https://orcid.org/0000-0001-5676-8527 ORCiD: Aaron R. Finney https://orcid.org/0000-0002-1456-5892 ORCiD: Joshua D. Elliott https://orcid.org/0000-0002-0729-246X ORCiD: Paola Carbone https://orcid.org/0000-0001-9927-8376 ORCiD; Matteo Salvalaglio https://orcid.org/0000-0003-3371-2090 134714 |
Appears in Collections: | Dept of Chemical Engineering Research Papers |
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FullText.pdf | Copyright © 2023 Author(s). The version available on this institutional repository is an uncorrected preprint made available under a Creative Commons (CC BY) Attribution License, and has not been peer reviewed This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Di Pasquale, N. et al. (2023) 'Constant chemical potential-quantum mechanical-molecular dynamics simulations of the graphene-electrolyte double layer', Journal of Chemical Physics, 158 (13), pp. 1 - 28., and may be found at https://doi.org/10.1063/5.0138267 (see: https://publishing.aip.org/resources/researchers/rights-and-permissions/sharing-content-online/. Please direct any questions to the Rights Office at rights@aip.org.). | 8.91 MB | Adobe PDF | View/Open |
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