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The influence of temperature and density functional models in ab initio molecular dynamics simulation of liquid water


VandeVondele, J; Mohamed, F; Krack, M; Hutter, J; Sprik, M; Parrinello, M (2005). The influence of temperature and density functional models in ab initio molecular dynamics simulation of liquid water. Journal of Chemical Physics, 122(1):014515.

Abstract

The performance of density functional theory methods for the modeling of condensed aqueous systems is hard to predict and validation by ab initio molecular simulation of liquid water is absolutely necessary. In order to assess the reliability of these tests, the effect of temperature on the structure and dynamics of liquid water has been characterized with 16 simulations of 20 ps in the temperature range of 280-380 K. We find a pronounced influence of temperature on the pair correlation functions and on the diffusion constant including nonergodic behavior on the time scale of the simulation in the lower temperature range (which includes ambient temperature). These observations were taken into account in a consistent comparison of a series of density functionals (BLYP, PBE, TPSS, OLYP, HCTH120, HCTH407). All simulations were carried out using an ab initio molecular dynamics approach in which wave functions are represented using Gaussians and the density is expanded in an auxiliary basis of plane waves. Whereas the first three functionals show similar behavior, it is found that the latter three functionals yield more diffusive dynamics and less structure.

The performance of density functional theory methods for the modeling of condensed aqueous systems is hard to predict and validation by ab initio molecular simulation of liquid water is absolutely necessary. In order to assess the reliability of these tests, the effect of temperature on the structure and dynamics of liquid water has been characterized with 16 simulations of 20 ps in the temperature range of 280-380 K. We find a pronounced influence of temperature on the pair correlation functions and on the diffusion constant including nonergodic behavior on the time scale of the simulation in the lower temperature range (which includes ambient temperature). These observations were taken into account in a consistent comparison of a series of density functionals (BLYP, PBE, TPSS, OLYP, HCTH120, HCTH407). All simulations were carried out using an ab initio molecular dynamics approach in which wave functions are represented using Gaussians and the density is expanded in an auxiliary basis of plane waves. Whereas the first three functionals show similar behavior, it is found that the latter three functionals yield more diffusive dynamics and less structure.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2005
Deposited On:26 Mar 2009 07:57
Last Modified:20 May 2016 11:54
Publisher:American Institute of Physics
ISSN:0021-9606
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:10.1063/1.1828433
Permanent URL: http://doi.org/10.5167/uzh-3176

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