Systematic Optimization of Water Models Using Liquid/Vapor Surface Tension Data
Systematic Optimization of Water Models Using Liquid/Vapor Surface Tension Data
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DOI：
10.1021/acs.jpcb.9b05455
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发表时间：
2019-08-15
影响因子：
3.3
通讯作者：
Wang, Lee-Ping
中科院分区：
文献类型：
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作者：
Qiu, Yudong;Nerenberg, Paul S.;Wang, Lee-Ping
在这项工作中，我们研究了对量子和自极化修正不太敏感的实验表面张力测量是否能够取代通常对汽化热的依赖作为拟合分子液体力场模型的实验参考数据。为了验证这一假设，我们开发了在ForceBalance优化过程中利用表面张力测量来确定三点和四点水模型TIP3P-ST和TIP4P-ST的修正参数所必需的拟合方案。我们发现，表面张力的引入导致了一个刚性的三点模型，该模型首次再现了水的最大密度的正确温度，但也导致了液体的过度结构和较不精确的输运性质。刚性四点TIP4P-ST模型对广泛的热力学和动力学性质具有很高的精度，与最近开发的四点水模型具有相似的性能。结果表明，表面张力总体上是一个有用的拟合性质，特别是当自极化修正或核量子修正不能像其他分子液体那样容易地用来修正汽化热时。
In this work, we investigate whether experimental surface tension measurements, which are less sensitive to quantum and self-polarization corrections, are able to replace the usual reliance on the heat of vaporization as experimental reference data for fitting force field models of molecular liquids. To test this hypothesis, we develop the fitting protocol necessary to utilize surface tension measurements in the ForceBalance optimization procedure to determine revised parameters for both three-point and four-point water models TIP3P-ST and TIP4P-ST. We find that the incorporation of surface tension in the fit results in a rigid three-point model that reproduces the correct temperature of maximum density of water for the first time but also leads to overstructuring of the liquid and less accurate transport properties. The rigid four-point TIP4P-ST model is highly accurate for a broad range of thermodynamic and kinetic properties, with similar performance compared to recently developed four-point water models. The results show surface tension to be a useful fitting property in general, especially when self-polarization corrections or nuclear quantum corrections are not readily available for correcting the heat of vaporization as is the case for other molecular liquids.