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On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures

Santra, B; Klimes, J; Tkatchenko, A; Alfè, D; Slater, B; Michaelides, A; Car, R; (2013) On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures. The Journal of Chemical Physics , 139 (15) , Article 154702. 10.1063/1.4824481. Green open access

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Abstract

Density-functional theory (DFT) has been widely used to study water and ice for at least 20 years. However, the reliability of different DFT exchange-correlation (xc) functionals for water remains a matter of considerable debate. This is particularly true in light of the recent development of DFT based methods that account for van der Waals (vdW) dispersion forces. Here, we report a detailed study with several xc functionals (semi-local, hybrid, and vdW inclusive approaches) on ice Ih and six proton ordered phases of ice. Consistent with our previous study [B. Santra, J. Klimeš, D. Alfè, A. Tkatchenko, B. Slater, A. Michaelides, R. Car, and M. Scheffler, Phys. Rev. Lett. 107, 185701 (2011)] which showed that vdW forces become increasingly important at high pressures, we find here that all vdW inclusive methods considered improve the relative energies and transition pressures of the high-pressure ice phases compared to those obtained with semi-local or hybrid xc functionals. However, we also find that significant discrepancies between experiment and the vdW inclusive approaches remain in the cohesive properties of the various phases, causing certain phases to be absent from the phase diagram. Therefore, room for improvement in the description of water at ambient and high pressures remains and we suggest that because of the stern test the high pressure ice phases pose they should be used in future benchmark studies of simulation methods for water.

Type: Article
Title: On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures
Location: United States
Open access status: An open access version is available from UCL Discovery
DOI: 10.1063/1.4824481
Publisher version: http://dx.doi.org/10.1063/1.4824481
Language: English
Additional information: Reprinted with permission from Santra, B; Klimes, J; Tkatchenko, A; Alfè, D; Slater, B; Michaelides, A; Car, R; (2013) On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures. The Journal of Chemical Physics, 139 (15), Article 154702. Copyright © 2013, American Institute of Physics.
UCL classification: UCL
UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Earth Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy
URI: https://discovery.ucl.ac.uk/id/eprint/1403276
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