Skip to main content

The individual and collective effects of exact exchange and dispersion interactions on the ab initio structure of liquid water

Author(s): DiStasio, Robert A. Jr.; Santra, Biswajit; Li, Zhaofeng; Wu, Xifan; Car, Roberto

Download
To refer to this page use: http://arks.princeton.edu/ark:/88435/pr18n65
Full metadata record
DC FieldValueLanguage
dc.contributor.authorDiStasio, Robert A. Jr.-
dc.contributor.authorSantra, Biswajit-
dc.contributor.authorLi, Zhaofeng-
dc.contributor.authorWu, Xifan-
dc.contributor.authorCar, Roberto-
dc.date.accessioned2020-10-30T18:33:46Z-
dc.date.available2020-10-30T18:33:46Z-
dc.date.issued2014-08-28en_US
dc.identifier.citationDiStasio, Robert A. Jr., Santra, Biswajit, Li, Zhaofeng, Wu, Xifan, Car, Roberto. (2014). The individual and collective effects of exact exchange and dispersion interactions on the ab initio structure of liquid water. The Journal of Chemical Physics, 141 (8), 084502 - 084502. doi:10.1063/1.4893377en_US
dc.identifier.issn0021-9606-
dc.identifier.urihttp://arks.princeton.edu/ark:/88435/pr18n65-
dc.description.abstractIn this work, we report the results of a series of density functional theory (DFT) based ab initio molecular dynamics (AIMD) simulations of ambient liquid water using a hierarchy of exchange-correlation (XC) functionals to investigate the individual and collective effects of exact exchange (Exx), via the PBE0 hybrid functional, non-local van der Waals/dispersion (vdW) interactions, via a fully self-consistent density-dependent dispersion correction, and an approximate treatment of nuclear quantum effects, via a 30 K increase in the simulation temperature, on the microscopic structure of liquid water. Based on these AIMD simulations, we found that the collective inclusion of Exx and vdW as resulting from a large-scale AIMD simulation of (H2O)128 significantly softens the structure of ambient liquid water and yields an oxygen-oxygen structure factor, SOO(Q), and corresponding oxygen-oxygen radial distribution function, gOO(r), that are now in quantitative agreement with the best available experimental data. This level of agreement between simulation and experiment demonstrated herein originates from an increase in the relative population of water molecules in the interstitial region between the first and second coordination shells, a collective reorganization in the liquid phase which is facilitated by a weakening of the hydrogen bond strength by the use of a hybrid XC functional, coupled with a relative stabilization of the resultant disordered liquid water configurations by the inclusion of non-local vdW/dispersion interactions. This increasingly more accurate description of the underlying hydrogen bond network in liquid water also yields higher-order correlation functions, such as the oxygen-oxygen-oxygen triplet angular distribution, POOO(θ), and therefore the degree of local tetrahedrality, as well as electrostatic properties, such as the effective molecular dipole moment, that are in much better agreement with experiment.en_US
dc.format.extent084502-1 - 084502-16en_US
dc.language.isoen_USen_US
dc.relation.ispartofThe Journal of Chemical Physicsen_US
dc.rightsFinal published version. Article is made available in OAR by the publisher's permission or policy.en_US
dc.titleThe individual and collective effects of exact exchange and dispersion interactions on the ab initio structure of liquid wateren_US
dc.typeJournal Articleen_US
dc.identifier.doidoi:10.1063/1.4893377-
dc.date.eissued2014-08-25en_US
dc.identifier.eissn1089-7690-
pu.type.symplectichttp://www.symplectic.co.uk/publications/atom-terms/1.0/journal-articleen_US

Files in This Item:
File Description SizeFormat 
1.4893377.pdf1.01 MBAdobe PDFView/Download


Items in OAR@Princeton are protected by copyright, with all rights reserved, unless otherwise indicated.