Centre for Molecular Simulation, Swinburne University of Technology, PO Box 218, Hawthorn, Victoria 3122, Australia.
J Chem Phys. 2013 Nov 21;139(19):194505. doi: 10.1063/1.4832381.
The ability of intermolecular potentials to correctly predict the thermodynamic properties of liquid water at a density of 0.998 g∕cm(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.
研究了在 298-650 K 的温度范围和 0.1-700 MPa 的压力范围内，分子间势是否能够正确预测密度为 0.998 g∕cm(3)的液态水的热力学性质。使用非极化 SPC∕E 和 TIP4P∕2005 势能，对液态水的压力、热压力系数、热膨胀系数、等温压缩率和绝热压缩率、等压热容和等容热容以及焦耳-汤姆逊系数进行了分子动力学模拟。将结果与实验数据和基于从头算的 Matsuoka-Clementi-Yoshimine 非加性（MCYna）[J. Li, Z. Zhou, and R. J. Sadus, J. Chem. Phys. 127, 154509 (2007)]势能的结果进行了比较，后者包含极化贡献。数据清楚地表明，SPC∕E 和 TIP4P∕2005 势能仅与实验定性一致，而极化的 MCYna 势能在实验不确定性范围内预测了一些性质。这突出了极化对准确预测水的热力学性质的重要性，特别是在 298 K 以上的温度下。
