Ab initio molecular dynamics study of water at constant pressure using converged basis sets and empirical dispersion corrections.

Zhonghua Ma, Yanli Zhang, Mark E. Tuckerman

Research output: Contribution to journalArticle

Abstract

It is generally believed that studies of liquid water using the generalized gradient approximation to density functional theory require dispersion corrections in order to obtain reasonably accurate structural and dynamical properties. Here, we report on an ab initio molecular dynamics study of water in the isothermal-isobaric ensemble using a converged discrete variable representation basis set and an empirical dispersion correction due to Grimme [J. Comp. Chem. 27, 1787 (2006)]. At 300 K and an applied pressure of 1 bar, the density obtained without dispersion corrections is approximately 0.92 g/cm(3) while that obtained with dispersion corrections is 1.07 g/cm(3), indicating that the empirical dispersion correction overestimates the density by almost as much as it is underestimated without the correction for this converged basis. Radial distribution functions exhibit a loss of structure in the second solvation shell. Comparison of our results with other studies using the same empirical correction suggests the cause of the discrepancy: the Grimme dispersion correction is parameterized for use with a particular basis set; this parameterization is sensitive to this choice and, therefore, is not transferable to other basis sets.

Original languageEnglish (US)
Pages (from-to)44506
Number of pages1
JournalJournal of Chemical Physics
Volume137
Issue number4
StatePublished - Jul 28 2012

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Molecular Dynamics Simulation
Molecular dynamics
molecular dynamics
Pressure
Water
water
Solvation
Parameterization
Distribution functions
Density functional theory
parameterization
radial distribution
solvation
distribution functions
Liquids
density functional theory
gradients
causes
liquids
approximation

ASJC Scopus subject areas

  • Medicine(all)

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Ab initio molecular dynamics study of water at constant pressure using converged basis sets and empirical dispersion corrections. / Ma, Zhonghua; Zhang, Yanli; Tuckerman, Mark E.

In: Journal of Chemical Physics, Vol. 137, No. 4, 28.07.2012, p. 44506.

Research output: Contribution to journalArticle

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