skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Intermolecular potentials and the accurate prediction of the thermodynamic properties of water

Abstract

The ability of intermolecular potentials to correctly predict the thermodynamic properties of liquid water at a density of 0.998 g/cm{sup 3} for a wide range of temperatures (298–650 K) and pressures (0.1–700 MPa) is investigated. Molecular dynamics simulations are reported for the pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, and Joule-Thomson coefficient of liquid water using the non-polarizable SPC/E and TIP4P/2005 potentials. The results are compared with both experiment data and results obtained from the ab initio-based Matsuoka-Clementi-Yoshimine non-additive (MCYna) [J. Li, Z. Zhou, and R. J. Sadus, J. Chem. Phys. 127, 154509 (2007)] potential, which includes polarization contributions. The data clearly indicate that both the SPC/E and TIP4P/2005 potentials are only in qualitative agreement with experiment, whereas the polarizable MCYna potential predicts some properties within experimental uncertainty. This highlights the importance of polarizability for the accurate prediction of the thermodynamic properties of water, particularly at temperatures beyond 298 K.

Authors:
Publication Date:
OSTI Identifier:
22251387
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 139; Journal Issue: 19; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPRESSIBILITY; DENSITY; FORECASTING; LIQUIDS; MOLECULAR DYNAMICS METHOD; POLARIZABILITY; POLARIZATION; PRESSURE COEFFICIENT; SIMULATION; SPECIFIC HEAT; THERMAL EXPANSION; WATER

Citation Formats

Shvab, I., and Sadus, Richard J., E-mail: rsadus@swin.edu.au. Intermolecular potentials and the accurate prediction of the thermodynamic properties of water. United States: N. p., 2013. Web. doi:10.1063/1.4832381.
Shvab, I., & Sadus, Richard J., E-mail: rsadus@swin.edu.au. Intermolecular potentials and the accurate prediction of the thermodynamic properties of water. United States. https://doi.org/10.1063/1.4832381
Shvab, I., and Sadus, Richard J., E-mail: rsadus@swin.edu.au. 2013. "Intermolecular potentials and the accurate prediction of the thermodynamic properties of water". United States. https://doi.org/10.1063/1.4832381.
@article{osti_22251387,
title = {Intermolecular potentials and the accurate prediction of the thermodynamic properties of water},
author = {Shvab, I. and Sadus, Richard J., E-mail: rsadus@swin.edu.au},
abstractNote = {The ability of intermolecular potentials to correctly predict the thermodynamic properties of liquid water at a density of 0.998 g/cm{sup 3} for a wide range of temperatures (298–650 K) and pressures (0.1–700 MPa) is investigated. Molecular dynamics simulations are reported for the pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, and Joule-Thomson coefficient of liquid water using the non-polarizable SPC/E and TIP4P/2005 potentials. The results are compared with both experiment data and results obtained from the ab initio-based Matsuoka-Clementi-Yoshimine non-additive (MCYna) [J. Li, Z. Zhou, and R. J. Sadus, J. Chem. Phys. 127, 154509 (2007)] potential, which includes polarization contributions. The data clearly indicate that both the SPC/E and TIP4P/2005 potentials are only in qualitative agreement with experiment, whereas the polarizable MCYna potential predicts some properties within experimental uncertainty. This highlights the importance of polarizability for the accurate prediction of the thermodynamic properties of water, particularly at temperatures beyond 298 K.},
doi = {10.1063/1.4832381},
url = {https://www.osti.gov/biblio/22251387}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 19,
volume = 139,
place = {United States},
year = {2013},
month = {11}
}