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Perspective: How good is DFT for water?

Gillan, MJ; Alfè, D; Michaelides, A; (2016) Perspective: How good is DFT for water? The Journal of Chemical Physics , 144 , Article 130901. 10.1063/1.4944633. Green open access

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Abstract

Kohn-Sham density functional theory (DFT) has become established as an indispensable tool for investigating aqueous systems of all kinds, including those important in chemistry, surface science, biology and the earth sciences. Nevertheless, many widely used approximations for the exchange-correlation (XC) functional describe the properties of pure water systems with an accuracy that is not fully satisfactory. The explicit inclusion of dispersion interactions generally improves the description, but there remain large disagreements between the predictions of different dispersion-inclusive methods. We present here a review of DFT work on water clusters, ice structures and liquid water, with the aim of elucidating how the strengths and weaknesses of different XC approximations manifest themselves across this variety of water systems. Our review highlights the crucial role of dispersion in describing the delicate balance between compact and extended structures of many different water systems, including the liquid. By referring to a wide range of published work, we argue that the correct description of exchange-overlap interactions is also extremely important, so that the choice of semi-local or hybrid functional employed in dispersion-inclusive methods is crucial. The origins and consequences of beyond-2-body errors of approximate XC functionals are noted, and we also discuss the substantial differences between different representations of dispersion. We propose a simple numerical scoring system that rates the performance of different XC functionals in describing water systems, and we suggest possible future developments.

Type: Article
Title: Perspective: How good is DFT for water?
Open access status: An open access version is available from UCL Discovery
DOI: 10.1063/1.4944633
Publisher version: http://dx.doi.org/10.1063/1.4944633
Language: English
Additional information: This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in: Gillan, MJ; Alfè, D; Michaelides, A; (2016) Perspective: How good is DFT for water? The Journal of Chemical Physics, 144, Article 130901, and may be found at: http://dx.doi.org/10.1063/1.4944633.
Keywords: cond-mat.mtrl-sci, cond-mat.mtrl-sci, physics.chem-ph
UCL classification: UCL
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 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/1477473
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