Practical Considerations for Finite Concentrations Molecular Dynamics Simulations
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arXiv
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| Format: | Preprint |
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2026
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| _version_ | 1866917220472324096 |
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| author | Ruan, Xiaoxu Roncoroni, Fabrice Prendergast, David Pascal, Tod A |
| author_facet | Ruan, Xiaoxu Roncoroni, Fabrice Prendergast, David Pascal, Tod A |
| contents | Understanding concentrated electrolytes requires a theory that spans local hydration and mesoscale interfacial assembly. We present an integrated workflow-SCOPE-that combines (i) enhanced sampling focused on a single Li+ ion, (ii) reweighting of biased trajectories to recover equilibrium microstate probabilities, and (iii) a chemical-potential correction that accounts for the limited reservoir of free water in finite simulation boxes. Applied to LiCl(aq) across 0.5-26 M and 283-313 K, this approach reveals a simple organizing principle: solvated ions dominate at low concentration; contact ion pairs emerge at intermediate strength; and aggregated Li-xCl clusters become most stable at the solubility limit. The resulting free-energy trends predict temperature-dependent solubility in close agreement with experiment and clarify the role of interfacial nucleation in precipitation. Beyond the simple LiCl(aq) salt considered here, SCOPE offers a transferable strategy for characterizing speciation and phase behavior in concentrated liquid systems where collective coordinates and rare events dominate. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2601_17244 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Practical Considerations for Finite Concentrations Molecular Dynamics Simulations Ruan, Xiaoxu Roncoroni, Fabrice Prendergast, David Pascal, Tod A Soft Condensed Matter Statistical Mechanics Atomic and Molecular Clusters Chemical Physics Understanding concentrated electrolytes requires a theory that spans local hydration and mesoscale interfacial assembly. We present an integrated workflow-SCOPE-that combines (i) enhanced sampling focused on a single Li+ ion, (ii) reweighting of biased trajectories to recover equilibrium microstate probabilities, and (iii) a chemical-potential correction that accounts for the limited reservoir of free water in finite simulation boxes. Applied to LiCl(aq) across 0.5-26 M and 283-313 K, this approach reveals a simple organizing principle: solvated ions dominate at low concentration; contact ion pairs emerge at intermediate strength; and aggregated Li-xCl clusters become most stable at the solubility limit. The resulting free-energy trends predict temperature-dependent solubility in close agreement with experiment and clarify the role of interfacial nucleation in precipitation. Beyond the simple LiCl(aq) salt considered here, SCOPE offers a transferable strategy for characterizing speciation and phase behavior in concentrated liquid systems where collective coordinates and rare events dominate. |
| title | Practical Considerations for Finite Concentrations Molecular Dynamics Simulations |
| topic | Soft Condensed Matter Statistical Mechanics Atomic and Molecular Clusters Chemical Physics |
| url | https://arxiv.org/abs/2601.17244 |