Density, structure, and dynamics of water: The effect of van der Waals interactions

Wang, Jue and Román-Pérez, G. and Soler, Jose M. and Artacho, Emilio and Fernández-Serra, M.-V. (2011) Density, structure, and dynamics of water: The effect of van der Waals interactions. The Journal of Chemical Physics, 134 (2). 024516. DOI

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It is known that ab initio molecular dynamics (AIMD) simulations of liquid water at ambient conditions, based on the generalized gradient approximation (GGA) to density functional theory (DFT), with commonly used functionals fail to produce structural and diffusive properties in reasonable agreement with experiment. This is true for canonical, constant temperature simulations where the density of the liquid is fixed to the experimental density. The equilibrium density, at ambient conditions, of DFT water has recently been shown by Schmidt et al. [J. Phys. Chem. B, 113, 11959 (2009)] to be underestimated by different GGA functionals for exchange and correlation, and corrected by the addition of interatomic pair potentials to describe van der Waals (vdW) interactions. In this contribution we present a DFT-AIMD study of liquid water using several GGA functionals as well as the van der Waals density functional (vdW-DF) of Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)]. As expected, we find that the density of water is grossly underestimated by GGA functionals. When a vdW-DF is used, the density improves drastically and the experimental diffusivity is reproduced without the need of thermal corrections. We analyze the origin of the density differences between all the functionals. We show that the vdW-DF increases the population of non-H-bonded interstitial sites, at distances between the first and second coordination shells. However, it excessively weakens the H-bond network, collapsing the second coordination shell. This structural problem is partially associated to the choice of GGA exchange in the vdW-DF. We show that a different choice for the exchange functional is enough to achieve an overall improvement both in structure and diffusivity.

Item Type: Article
Additional Information: Received 14 May 2010; accepted 6 November 2010; published online 12 January 2011; publisher error corrected 18 January 2011 Journal of Chemical Physics / Volume 134 / Issue 5 / LETTERS TO THE EDITOR / Errata / Back to Abstract Previous Article | Next Article Publisher's Note: “Density, structure, and dynamics of water: The effect of van der Waals interactions” [J. Chem. Phys. 134, 024516 (2011)] Jue Wang1, G. Román-Pérez2, Jose M. Soler2, Emilio Artacho3, and M.-V. Fernández-Serra1,4,a 1 Department of Physics and Astronomy, Stony Brook University, Stony Brook, New York 11794-3800, USA 2 Dep. de Física de la Materia Condensada, Universidad Autónoma de Madrid, 28049 Madrid, Spain 3 Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ, United Kingdom 4 New York Center for Computational Science, Stony Brook University, Stony Brook, New York 11794-3800, USA (Received 14 January 2011; published online 3 February 2011) This article was originally published online on 12 January 2011 with incorrect affiliation designations for Jose M. Soler and Emilio Artacho. AIP apologizes for these errors. The affiliation designations were correct in the printed version of the journal and appear correctly above. All online versions of the article were corrected on 18 January 2011.
Uncontrolled Keywords: 2010AREP; IA61;
Subjects: 03 - Mineral Sciences
Divisions: 03 - Mineral Sciences
Journal or Publication Title: The Journal of Chemical Physics
Volume: 134
Page Range: 024516
Identification Number:
Depositing User: Sarah Humbert
Date Deposited: 26 Feb 2011 12:22
Last Modified: 23 Jul 2013 10:01

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