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

Autor(en)

Biswajit Santra, Jiri Klimes, Alexandre Tkatchenko, Dario Alfe, Ben Slater, Angelos Michaelides, Roberto Car, Matthias Scheffler

Abstrakt

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.

Organisation(en)

Computergestützte Materialphysik

Externe Organisation(en)

Fritz-Haber-Institut der Max-Planck-Gesellschaft, Princeton University, University College London

Journal

Journal of Chemical Physics

Band

139

Anzahl der Seiten

11

ISSN

0021-9606

DOI

https://doi.org/10.1063/1.4824481

Publikationsdatum

10-2013

Peer-reviewed

Ja

ÖFOS 2012

103009 Festkörperphysik, 103015 Kondensierte Materie, 103025 Quantenmechanik, 103036 Theoretische Physik

Schlagwörter

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/4f99cbfd-8189-4ce0-a2cf-59e134b97e1b