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  4. Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions
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research article

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions

Miceli, Giacomo  
•
de Gironcoli, Stefano
•
Pasquarello, Alfredo  
2015
Journal Of Chemical Physics

We investigate the structural properties of liquid water at near ambient conditions using first-principles molecular dynamics simulations based on a semilocal density functional augmented with nonlocal van der Waals interactions. The adopted scheme offers the advantage of simulating liquid water at essentially the same computational cost of standard semilocal functionals. Applied to the water dimer and to ice I-h, we find that the hydrogen-bond energy is only slightly enhanced compared to a standard semilocal functional. We simulate liquid water through molecular dynamics in the N pH statistical ensemble allowing for fluctuations of the system density. The structure of the liquid departs from that found with a semilocal functional leading to more compact structural arrangements. This indicates that the directionality of the hydrogen-bond interaction has a diminished role as compared to the overall attractions, as expected when dispersion interactions are accounted for. This is substantiated through a detailed analysis comprising the study of the partial radial distribution functions, various local order indices, the hydrogen-bond network, and the selfdiffusion coefficient. The explicit treatment of the van der Waals interactions leads to an overall improved description of liquid water. (c) 2015 AIP Publishing LLC.

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Type
research article
DOI
10.1063/1.4905333
Web of Science ID

WOS:000348302900032

Author(s)
Miceli, Giacomo  
de Gironcoli, Stefano
Pasquarello, Alfredo  
Date Issued

2015

Publisher

American Institute of Physics

Published in
Journal Of Chemical Physics
Volume

142

Issue

3

Article Number

034501

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
CSEA  
Available on Infoscience
May 29, 2015
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/114711
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