Molecular modeling of aqueous electrolytes at interfaces: effects of long-range dispersion forces and of ionic charge rescaling
| Autor: | Guillaume Le Breton, Laurent Joly |
|---|---|
| Přispěvatelé: | Département de Physique [ENS Lyon], École normale supérieure de Lyon (ENS de Lyon)-Université de Lyon, Physico-chimie théorique (THEOCHEM), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Modélisation de la matière condensée et des interfaces (MMCI), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), ANR-16-CE06-0004,NECtAR,Interfaces réactives pour la conversion d'énergie nanofluidique(2016), École normale supérieure - Lyon (ENS Lyon)-Université de Lyon, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon |
| Rok vydání: | 2020 |
| Předmět: |
Chemical physics
General Physics and Astronomy Ionic bonding FOS: Physical sciences Condensed Matter - Soft Condensed Matter Molecular dynamics 010402 general chemistry Method of image charges 01 natural sciences London dispersion force Force field (chemistry) Surface tension Liquid-vapor interface Electrolytes [SPI]Engineering Sciences [physics] 0103 physical sciences Force field [CHIM]Chemical Sciences Physical and Theoretical Chemistry Physics [PHYS]Physics [physics] 010304 chemical physics Computational Physics (physics.comp-ph) Electrostatics 0104 chemical sciences Soft Condensed Matter (cond-mat.soft) Electric potential Physics - Computational Physics Surface tension studies |
| Zdroj: | Journal of Chemical Physics Journal of Chemical Physics, 2020, 152 (24), pp.241102. ⟨10.1063/5.0011058⟩ Journal of Chemical Physics, American Institute of Physics, 2020, 152 (24), pp.241102. ⟨10.1063/5.0011058⟩ |
| ISSN: | 0021-9606 1089-7690 |
| DOI: | 10.48550/arxiv.2004.07702 |
| Popis: | Molecular dynamics simulations of aqueous electrolytes generally rely on empirical force fields, combining dispersion interactions - described by a truncated Lennard-Jones (LJ) potential - and electrostatic interactions - described by a Coulomb potential computed with a long-range solver. Recently, force fields using rescaled ionic charges (electronic continuum correction, ECC), possibly complemented with rescaling of LJ parameters (electronic continuum correction rescaled, ECCR), have shown promising results in bulk, but their performance at interfaces has been less explored. Here we started by exploring the impact of the LJ potential truncation on the surface tension of a sodium chloride aqueous solution. We show a discrepancy between the numerical predictions for truncated LJ interactions with a large cutoff and for untruncated LJ interactions computed with a long-range solver, which can bias comparison of force field predictions with experiments. Using a long-range solver for LJ interactions, we then show that an ionic charge rescaling factor chosen to correct long-range electrostatic interactions in bulk also describes accurately image charge repulsion at the liquid-vapor interface, and that the rescaling of LJ parameters in ECCR models - aimed at capturing local ion-ion and ion-water interactions in bulk - also describes well the formation of an ionic double layer at the liquid-vapor interface. Overall, these results suggest that the molecular modeling of aqueous electrolytes at interfaces would benefit from using long-range solvers for dispersion forces, and from using ECCR models, where the charge rescaling factor should be chosen to correct long-range electrostatic interactions. Comment: Main text: 6 pages, 3 figures; Supplemental material: 9 pages, 3 figures; to be published in J. Chem. Phys |
| Databáze: | OpenAIRE |
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