Issue 19, 2020

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

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 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.

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

Article information

Article type
Paper
Submitted
14 ⵏⵓⵡ 2019
Accepted
09 ⴷⵓⵊ 2019
First published
19 ⴷⵓⵊ 2019

Phys. Chem. Chem. Phys., 2020,22, 10641-10652

Author version available

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

T. T. Duignan, G. K. Schenter, J. L. Fulton, T. Huthwelker, M. Balasubramanian, M. Galib, M. D. Baer, J. Wilhelm, J. Hutter, M. Del Ben, X. S. Zhao and C. J. Mundy, Phys. Chem. Chem. Phys., 2020, 22, 10641 DOI: 10.1039/C9CP06161D

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