Ab Initio van der Waals Interactions in Simulations of Water Alter Structure from Mainly Tetrahedral to High-Density-Like

Authors
Andreas Møgelhøj,
André K. Kelkkanen,
K. Thor Wikfeldt,
Jakob Schiøtz,
Jens Jørgen Mortensen,
Lars G. M. Pettersson,
Bengt I. Lundqvist,
Karsten W. Jacobsen,
Anders Nilsson,
Jens K. Nørskov
Year of publication
2011
Journal
The Journal of Physical Chemistry B
Issue
48
Volume
115
Starting page
14149
Ending page
14160
The structure of liquid water at ambient conditions is studied in ab initio molecular dynamics simulations in the NVE ensemble using van der Waals (vdW) density-functional theory, i.e., using the new exchange–correlation functionals optPBE-vdW and vdW-DF2, where the latter has softer nonlocal correlation terms. Inclusion of the more isotropic vdW interactions counteracts highly directional hydrogen bonds, which are enhanced by standard functionals. This brings about a softening of the microscopic structure of water, as seen from the broadening of angular distribution functions and, in particular, from the much lower and broader first peak in the oxygen–oxygen pair-correlation function (PCF) and loss of structure in the outer hydration shells. Inclusion of vdW interactions is shown to shift the balance of resulting structures from open tetrahedral to more close-packed. The resulting O–O PCF shows some resemblance with experiment for high-density water ( Soper, A. K. and Ricci, M. A. Phys. Rev. Lett. 2000, ...