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

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI: https://doi.org/10.1039/c9cp06161d · OSTI ID:1660541
ORCiD logo [1]; ORCiD logo [2];  [2];  [3];  [4]; ORCiD logo [2]; ORCiD logo [2];  [5];  [6];  [7]; ORCiD logo [8]; ORCiD logo [9]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Science Division; Univ. of Queensland, Brisbane, QLD (Australia). School of Chemical Engineering
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Science Division
  3. Paul Scherrer Inst. (PSI), Villigen (Switzerland). Swiss Light Source
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Univ. of Zurich (Switzerland). Dept. of Chemistry; Univ. of Regensburg (Germany). Inst. for Theoretical Physics
  6. Univ. of Zurich (Switzerland). Dept. of Chemistry
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division
  8. Univ. of Queensland, Brisbane, QLD (Australia). School of Chemical Engineering
  9. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Science Division; Univ. of Washington, Seattle, WA (United States). Dept. of Chemical Engineering
+ Show Author Affiliations

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. In this study, 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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
Australian Research Council (ARC); Swiss National Science Foundation (SNSF); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357; AC05-76RL01830
OSTI ID:
1660541
Report Number(s):
PNNL-SA--140415; 159044
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 19 Vol. 22; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Late Postoperative Cardiac Tamponade Presenting as a Pulsatile Epigastric Mass journal January 1993
Similarities and differences between potassium and ammonium ions in liquid water: a first-principles study journal January 2020
Temperature effects on the ionic conductivity in concentrated alkaline electrolyte solutions journal January 2020
Temperature effects on the ionic conductivity in concentrated alkaline electrolyte solutions text January 2019

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