Comparative molecular dynamics simulations of charged solid-liquid interfaces with different water models
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arXiv
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| Format: | Preprint |
| Publié: |
2025
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| _version_ | 1866911100178530304 |
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| author | Tavakol, Mahdi Voïtchovsky, Kislon |
| author_facet | Tavakol, Mahdi Voïtchovsky, Kislon |
| contents | Aqueous solid-liquid interfaces (SLI) are ubiquitous in nature and technology, often hosting molecular-level processes with macroscopic consequences. Molecular dynamics (MD) simulations offer a tool of choice to investigate interfacial phenomena with atomistic precision, but there exists a large number of water models, each optimised for a different purpose. Here we compare the ability of common water models to accurately simulate the interface between a charged silica surface and an aqueous solution containing NaCl. We first compare the bulk dielectric constant of water and its dependence on salt concentration for SPC/Fw, SPC/e, TIPS3p, H2O/DC, TIP3P-Fw, OPC3, TIP3P, TIP3P-FB, TIP3P-ST, FBA/e, and TIPS3p-PPPM, revealing large variations between models. Simulating the interface with silica for the most suitable water models (SPC/Fw, H2O/DC, TIP3-ST and TIPS3p-PPPM) show some intrinsic consistency with continuum predictions (Poisson-Boltzmann) whereby the free energy minima obtained from MD and the analytical model are in agreement, provided the latter includes the MD-determined total charge of ions in the Stern layer and dielectric constant. This consistency stands even for water models with a dielectric constant off by 100%. For salt concentrations higher than 0.21 M NaCl, the formation of random ion-ion pairs limits the reproducibility of the MD results and the applicability of the analytical method. The results highlight the applicability of the analytical model down to the nanoscale, provided a priory knowledge of the Stern layer charge is available. The findings could have significant implications for MD simulations of SLIs, especially at charged or electrified interfaces. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2508_02170 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Comparative molecular dynamics simulations of charged solid-liquid interfaces with different water models Tavakol, Mahdi Voïtchovsky, Kislon Soft Condensed Matter Statistical Mechanics Aqueous solid-liquid interfaces (SLI) are ubiquitous in nature and technology, often hosting molecular-level processes with macroscopic consequences. Molecular dynamics (MD) simulations offer a tool of choice to investigate interfacial phenomena with atomistic precision, but there exists a large number of water models, each optimised for a different purpose. Here we compare the ability of common water models to accurately simulate the interface between a charged silica surface and an aqueous solution containing NaCl. We first compare the bulk dielectric constant of water and its dependence on salt concentration for SPC/Fw, SPC/e, TIPS3p, H2O/DC, TIP3P-Fw, OPC3, TIP3P, TIP3P-FB, TIP3P-ST, FBA/e, and TIPS3p-PPPM, revealing large variations between models. Simulating the interface with silica for the most suitable water models (SPC/Fw, H2O/DC, TIP3-ST and TIPS3p-PPPM) show some intrinsic consistency with continuum predictions (Poisson-Boltzmann) whereby the free energy minima obtained from MD and the analytical model are in agreement, provided the latter includes the MD-determined total charge of ions in the Stern layer and dielectric constant. This consistency stands even for water models with a dielectric constant off by 100%. For salt concentrations higher than 0.21 M NaCl, the formation of random ion-ion pairs limits the reproducibility of the MD results and the applicability of the analytical method. The results highlight the applicability of the analytical model down to the nanoscale, provided a priory knowledge of the Stern layer charge is available. The findings could have significant implications for MD simulations of SLIs, especially at charged or electrified interfaces. |
| title | Comparative molecular dynamics simulations of charged solid-liquid interfaces with different water models |
| topic | Soft Condensed Matter Statistical Mechanics |
| url | https://arxiv.org/abs/2508.02170 |