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Ion-specific hydration structures revealed by SCAN-based ab initio simulations |
| Tiancheng Liang(梁天成)1,†, Liying Zhou(周丽颖)1,2,†, Yizhi Song(宋易知)1,3,†, Xifan Wu3,4, and Limei Xu(徐莉梅)1,5,6,‡ |
1 International Center for Quantum Materials, School of Physics, Peking University, Beijing 100871, China;
2 Postdoctoral Research Station of China CITIC Bank, Beijing 100026, China;
3 Department of Physics, Temple University, Philadelphia, Pennsylvania 19122, United States;
4 Institute for Computational Molecular Science, Temple University, Philadelphia, Pennsylvania 19122, United States;
5 Interdisciplinary Institute of Light-Element Quantum Materials and Research Center for Light-Element Advanced Materials, Peking University, Beijing 100871, China;
6 Collaborative Innovation Center of Quantum Matter, Beijing 100871, China |
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Abstract Hydrated ions play essential roles in diverse chemical and biological processes, yet accurately characterizing their hydration structures remains challenging due to the delicate interplay of ion-water and water-water interactions. Here, we use ab initio molecular dynamics (AIMD) simulations based on the strongly constrained and appropriately normed (SCAN) exchange-correlation functional to systematically investigate the hydration structures of eight representative ions (Mg$^{2+}$, Ca$^{2+}$, Li$^{+}$, Na$^{+}$, K$^{+}$, F$^{-}$, Cl$^{-}$, Br$^{-})$ in aqueous solution. Compared to the widely used Perdew-Burke-Ernzerhof (PBE) functional, SCAN substantially improves the description of solvent water by weakening the hydrogen-bond network and enhancing structural disorder, yielding results in closer agreement with experiments. SCAN modifies ionic hydration shells in an ion-specific manner, governed by ionic size and charge, and reproduces experimental hydration geometries especially well for intermediate-size monovalent ions (Na$^{+}$, Cl$^{-}$). Moreover, SCAN consistently reduces the overpolarization of water molecules near ions. These improvements lead to more accurate and physically consistent hydration structures, highlighting SCAN's utility for modeling complex aqueous systems and offering guidance for future studies of ionic solvation.
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Received: 22 July 2025
Revised: 28 September 2025
Accepted manuscript online: 14 October 2025
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PACS:
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61.20.Qg
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(Structure of associated liquids: electrolytes, molten salts, etc.)
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31.15.eg
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(Exchange-correlation functionals (in current density functional theory))
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02.70.Ns
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(Molecular dynamics and particle methods)
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82.20.Wt
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(Computational modeling; simulation)
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| Fund: This project was supported by the National Natural Science Foundation of China (Grant Nos. 12535001, 11935002, and 11525520) and the National Key Research and Development Program of China (Grant No. 2021YFA1400500). |
Corresponding Authors:
Limei Xu
E-mail: limei.xu@pku.edu.cn
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Cite this article:
Tiancheng Liang(梁天成), Liying Zhou(周丽颖), Yizhi Song(宋易知), Xifan Wu, and Limei Xu(徐莉梅) Ion-specific hydration structures revealed by SCAN-based ab initio simulations 2025 Chin. Phys. B 34 126102
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