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Implicit Solvation Methods for Catalysis at Electrified Interfaces

[Image: see text] Implicit solvation is an effective, highly coarse-grained approach in atomic-scale simulations to account for a surrounding liquid electrolyte on the level of a continuous polarizable medium. Originating in molecular chemistry with finite solutes, implicit solvation techniques are...

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Autores principales: Ringe, Stefan, Hörmann, Nicolas G., Oberhofer, Harald, Reuter, Karsten
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9227731/
https://www.ncbi.nlm.nih.gov/pubmed/34928131
http://dx.doi.org/10.1021/acs.chemrev.1c00675
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author Ringe, Stefan
Hörmann, Nicolas G.
Oberhofer, Harald
Reuter, Karsten
author_facet Ringe, Stefan
Hörmann, Nicolas G.
Oberhofer, Harald
Reuter, Karsten
author_sort Ringe, Stefan
collection PubMed
description [Image: see text] Implicit solvation is an effective, highly coarse-grained approach in atomic-scale simulations to account for a surrounding liquid electrolyte on the level of a continuous polarizable medium. Originating in molecular chemistry with finite solutes, implicit solvation techniques are now increasingly used in the context of first-principles modeling of electrochemistry and electrocatalysis at extended (often metallic) electrodes. The prevalent ansatz to model the latter electrodes and the reactive surface chemistry at them through slabs in periodic boundary condition supercells brings its specific challenges. Foremost this concerns the difficulty of describing the entire double layer forming at the electrified solid–liquid interface (SLI) within supercell sizes tractable by commonly employed density functional theory (DFT). We review liquid solvation methodology from this specific application angle, highlighting in particular its use in the widespread ab initio thermodynamics approach to surface catalysis. Notably, implicit solvation can be employed to mimic a polarization of the electrode’s electronic density under the applied potential and the concomitant capacitive charging of the entire double layer beyond the limitations of the employed DFT supercell. Most critical for continuing advances of this effective methodology for the SLI context is the lack of pertinent (experimental or high-level theoretical) reference data needed for parametrization.
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spelling pubmed-92277312022-06-25 Implicit Solvation Methods for Catalysis at Electrified Interfaces Ringe, Stefan Hörmann, Nicolas G. Oberhofer, Harald Reuter, Karsten Chem Rev [Image: see text] Implicit solvation is an effective, highly coarse-grained approach in atomic-scale simulations to account for a surrounding liquid electrolyte on the level of a continuous polarizable medium. Originating in molecular chemistry with finite solutes, implicit solvation techniques are now increasingly used in the context of first-principles modeling of electrochemistry and electrocatalysis at extended (often metallic) electrodes. The prevalent ansatz to model the latter electrodes and the reactive surface chemistry at them through slabs in periodic boundary condition supercells brings its specific challenges. Foremost this concerns the difficulty of describing the entire double layer forming at the electrified solid–liquid interface (SLI) within supercell sizes tractable by commonly employed density functional theory (DFT). We review liquid solvation methodology from this specific application angle, highlighting in particular its use in the widespread ab initio thermodynamics approach to surface catalysis. Notably, implicit solvation can be employed to mimic a polarization of the electrode’s electronic density under the applied potential and the concomitant capacitive charging of the entire double layer beyond the limitations of the employed DFT supercell. Most critical for continuing advances of this effective methodology for the SLI context is the lack of pertinent (experimental or high-level theoretical) reference data needed for parametrization. American Chemical Society 2021-12-20 2022-06-22 /pmc/articles/PMC9227731/ /pubmed/34928131 http://dx.doi.org/10.1021/acs.chemrev.1c00675 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Ringe, Stefan
Hörmann, Nicolas G.
Oberhofer, Harald
Reuter, Karsten
Implicit Solvation Methods for Catalysis at Electrified Interfaces
title Implicit Solvation Methods for Catalysis at Electrified Interfaces
title_full Implicit Solvation Methods for Catalysis at Electrified Interfaces
title_fullStr Implicit Solvation Methods for Catalysis at Electrified Interfaces
title_full_unstemmed Implicit Solvation Methods for Catalysis at Electrified Interfaces
title_short Implicit Solvation Methods for Catalysis at Electrified Interfaces
title_sort implicit solvation methods for catalysis at electrified interfaces
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9227731/
https://www.ncbi.nlm.nih.gov/pubmed/34928131
http://dx.doi.org/10.1021/acs.chemrev.1c00675
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