Duignan, Timothy T. and Schenter, Gregory K. and Fulton, John L. and Huthwelker, Thomas and Balasubramanian, Mahalingam and Galib, Mirza and Baer, Marcel D. and Wilhelm, Jan and Hutter, Jurg and Del Ben, Mauro and 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. ISSN 1463-9076, 1463-9084
Full text not available from this repository. (Request a copy)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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | GENERALIZED GRADIENT APPROXIMATION; CORRELATED MOLECULAR CALCULATIONS; DENSITY-FUNCTIONAL THEORY; GAUSSIAN-BASIS SETS; I-TTM MODEL; LIQUID WATER; DYNAMICS; SOLVATION; SIMULATIONS; ALKALI; |
| Subjects: | 500 Science > 530 Physics |
| Divisions: | Physics > Institute of Theroretical Physics Physics > Institute of Theroretical Physics > Chair Professor Grifoni > Group Ferdinand Evers |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 23 Mar 2021 11:36 |
| Last Modified: | 23 Mar 2021 11:36 |
| URI: | https://pred.uni-regensburg.de/id/eprint/44537 |
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