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Duignan, Timothy T. ; Schenter, Gregory K. ; Fulton, John L. ; Huthwelker, Thomas ; Balasubramanian, Mahalingam ; Galib, Mirza ; Baer, Marcel D. ; Wilhelm, Jan ; Hutter, Jürg ; Del Ben, Mauro ; Zhao, X. S. ; Mundy, Christopher J.

Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder

Article

Duignan, Timothy T., Schenter, Gregory K., Fulton, John L., Huthwelker, Thomas, Balasubramanian, Mahalingam, Galib, Mirza, Baer, Marcel D., Wilhelm, Jan , Hutter, Jürg, Del Ben, Mauro, Zhao, X. S. and Mundy, Christopher J. (2020) Quantifying the hydration structure of sodium and potassium ions: taking additional steps on Jacob's Ladder. Physical Chemistry Chemical Physics 22 (19), pp. 10641-10652.

DOI to cite this document: 10.5283/epub.45957


Abstract

The ability to reproduce the experimental structure of water around the sodium and potassium ions is a key test of the quality of interaction potentials due to the central importance of these ions in a wide range of important phenomena. Here, we simulate the Na+ and K+ ions in bulk water using three density functional theory functionals: (1) the generalized gradient approximation (GGA) based ...

The ability to reproduce the experimental structure of water around the sodium and potassium ions is a key test of the quality of interaction potentials due to the central importance of these ions in a wide range of important phenomena. Here, we simulate the Na+ and K+ ions in bulk water using three density functional theory functionals: (1) the generalized gradient approximation (GGA) based dispersion corrected revised Perdew, Burke, and Ernzerhof functional (revPBE-D3) (2) the recently developed strongly constrained and appropriately normed (SCAN) functional (3) the random phase approximation (RPA) functional for potassium. We compare with experimental X-ray diffraction (XRD) and X-ray absorption fine structure (EXAFS) measurements to demonstrate that SCAN accurately reproduces key structural details of the hydration structure around the sodium and potassium cations, whereas revPBE-D3 fails to do so. However, we show that SCAN provides a worse description of pure water in comparison with revPBE-D3. RPA also shows an improvement for K+, but slow convergence prevents rigorous comparison. Finally, we analyse cluster energetics to show SCAN and RPA have smaller fluctuations of the mean error of ion–water cluster binding energies compared with revPBE-D3.



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Details

Item typeArticle
Journal or Publication TitlePhysical Chemistry Chemical Physics
Open Access TypeDue to SHERPA/RoMEO
Volume22
Number of Issue or Book Chapter19
Page Rangepp. 10641-10652
Date19 December 2020
Date of publication08 Jun 2021 12:40
InstitutionsPhysics > Institute of Theroretical Physics > Chair Ferdinand Evers
Identification Number
ValueType
10.1039/C9CP06161DDOI
Dewey Decimal Classification500 Science > 530 Physics
StatusPublished
RefereedYes, this version has been refereed
Created at the University of RegensburgYes
URN of the UB Regensburgurn:nbn:de:bvb:355-epub-459573
Item ID45957

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