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Title: Re-Examining the Properties of the Aqueous Vapor-Liquid Interface Using Dispersion Corrected Density Functional Theory

Abstract

First-principles molecular dynamics simulations, in which the forces are computed from electronic structure calculations, have great potential to provide unique insight into structure, dynamics, electronic properties, and chemistry at aqueous interfaces that is not available from empirical force fields. The majority of current first-principles simulations are driven by forces derived from density functional theory with generalized gradient approximations to the exchange-correlation energy, which do not capture dispersion interactions. We have carried out first-principles molecular dynamics simulations of air-water interfaces employing a particular generalized gradient approximation to the exchange-correlation functional (BLYP), with and without empirical dispersion corrections. We assess the utility of the dispersion corrections by comparison of a variety of structural, dynamic, and thermodynamic properties of bulk and interfacial water with experimental data, as well as other first-principles and force field-based simulations. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1030443
Report Number(s):
PNNL-SA-79783
Journal ID: ISSN 0021-9606; JCPSA6; KC0301020; TRN: US201124%%204
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 135; Journal Issue: 12; Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; APPROXIMATIONS; CHEMISTRY; ELECTRONIC STRUCTURE; FUNCTIONALS; THERMODYNAMIC PROPERTIES; WATER; MOLECULAR-DYNAMICS SIMULATIONS; WATER-SURFACE; AMBIENT CONDITIONS; 1ST PRINCIPLES; AIR/WATER INTERFACE; CANONICAL ENSEMBLE; ION SOLVATION; SPECTROSCOPY; GENERATION; DIFFUSION

Citation Formats

Baer, Marcel D., Mundy, Christopher J., McGrath, Matthew J., Kuo, I-F W., Siepmann, Joern I., and Tobias, Douglas J. Re-Examining the Properties of the Aqueous Vapor-Liquid Interface Using Dispersion Corrected Density Functional Theory. United States: N. p., 2011. Web. doi:10.1063/1.3633239.
Baer, Marcel D., Mundy, Christopher J., McGrath, Matthew J., Kuo, I-F W., Siepmann, Joern I., & Tobias, Douglas J. Re-Examining the Properties of the Aqueous Vapor-Liquid Interface Using Dispersion Corrected Density Functional Theory. United States. doi:10.1063/1.3633239.
Baer, Marcel D., Mundy, Christopher J., McGrath, Matthew J., Kuo, I-F W., Siepmann, Joern I., and Tobias, Douglas J. Wed . "Re-Examining the Properties of the Aqueous Vapor-Liquid Interface Using Dispersion Corrected Density Functional Theory". United States. doi:10.1063/1.3633239.
@article{osti_1030443,
title = {Re-Examining the Properties of the Aqueous Vapor-Liquid Interface Using Dispersion Corrected Density Functional Theory},
author = {Baer, Marcel D. and Mundy, Christopher J. and McGrath, Matthew J. and Kuo, I-F W. and Siepmann, Joern I. and Tobias, Douglas J.},
abstractNote = {First-principles molecular dynamics simulations, in which the forces are computed from electronic structure calculations, have great potential to provide unique insight into structure, dynamics, electronic properties, and chemistry at aqueous interfaces that is not available from empirical force fields. The majority of current first-principles simulations are driven by forces derived from density functional theory with generalized gradient approximations to the exchange-correlation energy, which do not capture dispersion interactions. We have carried out first-principles molecular dynamics simulations of air-water interfaces employing a particular generalized gradient approximation to the exchange-correlation functional (BLYP), with and without empirical dispersion corrections. We assess the utility of the dispersion corrections by comparison of a variety of structural, dynamic, and thermodynamic properties of bulk and interfacial water with experimental data, as well as other first-principles and force field-based simulations. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.},
doi = {10.1063/1.3633239},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 12,
volume = 135,
place = {United States},
year = {2011},
month = {9}
}