Ion-specific hydration structures revealed by SCAN-based ab initio simulations

doi:10.1088/1674-1056/ae12d2

中国物理B ›› 2025, Vol. 34 ›› Issue (12): 126102-126102.doi: 10.1088/1674-1056/ae12d2

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 Wu^3,4, 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

收稿日期:2025-07-22 修回日期:2025-09-28 接受日期:2025-10-14 发布日期:2025-12-10
通讯作者: Limei Xu E-mail:limei.xu@pku.edu.cn
基金资助:
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).

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 Wu^3,4, 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

Received:2025-07-22 Revised:2025-09-28 Accepted:2025-10-14 Published:2025-12-10
Contact: Limei Xu E-mail:limei.xu@pku.edu.cn
Supported by:
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).

摘要/Abstract

摘要： 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.

关键词: ion hydration, solvent structure, SCAN functional, ab initio molecular dynamics

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.

Key words: ion hydration, solvent structure, SCAN functional, ab initio molecular dynamics

中图分类号: (Structure of associated liquids: electrolytes, molten salts, etc.)

61.20.Qg

31.15.eg (Exchange-correlation functionals (in current density functional theory)) 02.70.Ns (Molecular dynamics and particle methods) 82.20.Wt (Computational modeling; simulation)

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[J]. 中国物理B, 2025, 34(12): 126102-126102.

参考文献

[1] Cohen-Tanugi D and Grossman J C 2012 Nano Lett. 12 3602
[2] Sipila M, Sarnela N, Jokinen T, et al. 2016 Nature 537 532
[3] Klimes J, Bowler D R and Michaelides A 2013 J. Chem. Phys. 139 234702
[4] Gouaux E and Mackinnon R 2005 Science 310 1461
[5] Payandeh J, Scheuer T, Zheng N and Catterall W A 2011 Nature 475 353
[6] Smirnov P R and Trostin V N 2007 Russ. J. Gen. Chem. 77 844
[7] Smirnov P R and Trostin V N 2009 Russ. J. Gen. Chem. 79 1600
[8] Smirnov P R and Trostin V N 2007 Russ. J. Gen. Chem. 77 2101
[9] Swartz C W and Wu X 2013 Phys. Rev. Lett. 111 087801
[10] Tang F, Xu J, Qiu D Y and Wu X 2021 Phys. Rev. B 104 035117
[11] Probst M M, Radnai T, Heinzinger K, Bopp P and Rode B M 1985 J. Phys. Chem. 89 753
[12] Mahler J and Persson I 2012 Inorg. Chem. 51 425
[13] Martinek T, Duboue-Dijon E, Timr S, et al. 2018 J. Chem. Phys. 148 222813
[14] Gillan M J, Alfe D and Michaelides A 2016 J. Chem. Phys. 144 130901
[15] Licheri G, Piccaluga G and Pinna G 1976 J. Chem. Phys. 64 2437
[16] Soper A K and Weckstrom K 2006 Biophys. Chem. 124 180
[17] Skipper N T and Neilson G W 1989 J. Phys.: Condens. Matter 1 4141
[18] Mason P E, Ansell S and Neilson G W 2006 J. Phys.: Condens. Matter 18 8437
[19] Galib M, Baer M D, Skinner L B, et al. 2017 J. Chem. Phys. 146 084504
[20] Dang L X, Schenter G K, Glezakou V A and Fulton J L 2006 J. Phys. Chem. B 110 23644
[21] Kulik H J, Marzari N, Correa A A, et al. 2010 J. Phys. Chem. B 114 9594
[22] Naslund L A, Edwards D C, Wernet P, et al. 2005 J. Phys. Chem. A 109 5995
[23] Bian H, Wen X, Li J, et al. 2011 Proc. Natl. Acad. Sci. USA 108 4737
[24] Bian H, Li J, Zhang Q, et al. 2012 J. Phys. Chem. B 116 14426
[25] Peng J, Cao D, He Z, et al. 2018 Nature 557 701
[26] Tian Y, Huang B, Song Y, et al. 2024 Nat. Commun. 15 7834
[27] Tian Y, Song Y, Xia Y, et al. 2024 Nat. Nanotechnol. 19 479
[28] Car R and Parrinello M 1985 Phys. Rev. Lett. 55 2471
[29] Kresse G and Hafner J 1993 Phys. Rev. B 47 558
[30] Distasio Jr R A, Santra B, Li Z, Wu X and Car R 2014 J. Chem. Phys. 141 084502
[31] Zhou L, Xu J, Xu L and Wu X 2019 J. Chem. Phys. 150 124505
[32] Sun J, Ruzsinszky A and Perdew J P 2015 Phys. Rev. Lett. 115 036402
[33] Sun J, Remsing R C, Zhang Y, et al. 2016 Nat. Chem. 8 831
[34] Chen M, Ko H Y, Remsing R C, et al. 2017 Proc. Natl. Acad. Sci. USA 114 10846
[35] Giannozzi P, Andreussi O, Brumme T, et al. 2017 J. Phys.: Condens. Matter 29 465901
[36] Giannozzi P, Baroni S, Bonini N, et al. 2009 J. Phys.: Condens. Matter 21 395502
[37] Bankura A, Santra B, Distasio Jr R A, et al. 2015 Mol. Phys. 113 2842
[38] Pham T A, Ogitsu T, Lau E Y and Schwegler E 2016 J. Chem. Phys. 145 154501
[39] Xu J, Sun Z, Zhang C, et al. 2021 Phys. Rev. Mater. 5 L012801
[40] Hamann D R, Schluter M and Chiang C 1979 Phys. Rev. Lett. 43 1494
[41] Vanderbilt D 1985 Phys. Rev. B 32 8412
[42] Hamann D R 2013 Phys. Rev. B 88 085117
[43] Schlipf M and Gygi F 2015 Comput. Phys. Commun. 196 36
[44] Nose S 1984 J. Chem. Phys. 81 511
[45] Hoover W G 1985 Phys. Rev. A 31 1695
[46] Sun Z, Zheng L, Chen M, et al. 2018 Phys. Rev. Lett. 121 137401
[47] Bankura A, Vincenzo C and Klein M L 2014 Mol. Phys. 112 1448
[48] Payne M C, Teter M P, Allan D C, Arias T A and Joannopoulos J D 1992 Rev. Mod. Phys. 64 1045
[49] Grossman J C, Schwegler E, Draeger E W, Gygi F and Galli G 2004 J. Chem. Phys. 120 300
[50] Schwegler E, Grossman J C, Gygi F and Galli G 2004 J. Chem. Phys. 121 5400
[51] Gaiduk A P, Zhang C, Gygi F and Galli G 2014 Chem. Phys. Lett. 604 89
[52] Soper A K and Benmore C J 2008 Phys. Rev. Lett. 101 065502
[53] Marzari N and Vanderbilt D 1997 Phys. Rev. B 56 12847
[54] Silvestrelli P L, Marzari N, Vanderbilt D and Parrinello M 1998 Solid State Commun. 107 7
[55] Luzar A and Chandler D 1996 Phys. Rev. Lett. 76 928
[56] Tang F, Shi K and Wu X 2023 J. Chem. Phys. 159 164502
[57] Lightstone F C, Schwegler E, Hood R Q, Gygi F and Galli G 2001 Chem. Phys. Lett. 343 549
[58] Marcus Y 1983 J. Solution Chem. 12 271
[59] Badyal Y S, Saboungi M L, Price D L, et al. 2000 J. Chem. Phys. 112 9206
[60] Marcus Y 2009 Chem. Rev. 109 1346
[61] Zhang L, Han J, Wang H, Car R and E W 2018 Phys. Rev. Lett. 120 143001
[62] Vinogradov E V, Smirnov P R and Trostin V N 2003 Russ. Chem. Bull. 52 1253
[63] Glezakou V A, Chen Y, Fulton J L, Schenter G K and Dang L X 2006 Theor. Chem. Acc. 115 86

Ion-specific hydration structures revealed by SCAN-based ab initio simulations

Ion-specific hydration structures revealed by SCAN-based ab initio simulations

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 6

Metrics

本文评价

推荐阅读 0

[1]	Yong-Peng Shi(时永鹏), Ming-Feng Liu(刘鸣凤), Yun Chen(陈云), Wen-Lin Mo(莫文林), Dian-Zhong Li(李殿中), Tao Fa(法涛), Bin Bai(白彬), Xiao-Lin Wang(汪小琳), and Xing-Qiu Chen(陈星秋). Ab initio study of dynamical properties of U-Nb alloy melt[J]. 中国物理B, 2021, 30(12): 126105-126105.
[2]	张庆印, 谢鹏, 王欣, 于学文, 时志强, 赵世怀. Thermodynamic and transport properties of spiro-(1,1')-bipyrrolidinium tetrafluoroborate and acetonitrile mixtures: A molecular dynamics study[J]. 中国物理B, 2016, 25(6): 66102-066102.
[3]	索鎏敏, 方铮, 胡勇胜, 陈立泉. FT-Raman spectroscopy study of solvent-in-salt electrolytes[J]. 中国物理B, 2016, 25(1): 16101-016101.
[4]	Amani Tahat, Jordi Marti, Ali Khwaldeh, Kaher Tahat. Pattern recognition and data mining software based on artificial neural networks applied to proton transfer in aqueous environments[J]. 中国物理B, 2014, 23(4): 46101-046101.
[5]	顾斌, 张丰收, 黄余改, 方夏. Variations of water's local-structure induced by solvation of NaCl[J]. 中国物理B, 2010, 19(3): 36101-036101.
[6]	Dingding Lv(吕丁丁), Shuai Zhou(周帅), Kaipeng Liu(柳开鹏), Shiwei Dai(戴士为), and Lixin Ge(葛力新). Effects of the buffer layer on the Casimir pressure of peptide films deposited on a substrate[J]. 中国物理B, 2025, 34(10): 104202-104202.