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采用分子模拟预测水及其与甲醇和乙醇二元混合物的自扩散系数和剪切黏度。

Prediction of self-diffusion coefficient and shear viscosity of water and its binary mixtures with methanol and ethanol by molecular simulation.

机构信息

Laboratory for Engineering Thermodynamics, University of Kaiserslautern, Kaiserslautern, Germany.

出版信息

J Chem Phys. 2011 Feb 21;134(7):074508. doi: 10.1063/1.3515262.

Abstract

Density, self-diffusion coefficient, and shear viscosity of pure liquid water are predicted for temperatures between 280 and 373 K by molecular dynamics simulation and the Green-Kubo method. Four different rigid nonpolarizable water models are assessed: SPC, SPC/E, TIP4P, and TIP4P/2005. The pressure dependence of the self-diffusion coefficient and the shear viscosity for pure liquid water is also calculated and the anomalous behavior of these properties is qualitatively well predicted. Furthermore, transport properties as well as excess volume and excess enthalpy of aqueous binary mixtures containing methanol or ethanol, based on the SPC/E and TIP4P/2005 water models, are calculated. Under the tested conditions, the TIP4P/2005 model gives the best quantitative and qualitative agreement with experiments for the regarded transport properties. The deviations from experimental data are of 5% to 15% for pure liquid water and 5% to 20% for the water + alcohol mixtures. Moreover, the center of mass power spectrum of water as well as the investigated mixtures are analyzed and the hydrogen-bonding structure is discussed for different states.

摘要

采用分子动力学模拟和格林-库伯方法预测了 280 至 373 K 温度范围内纯液态水的密度、自扩散系数和剪切黏度。评估了四种不同的刚性非极化水分子模型:SPC、SPC/E、TIP4P 和 TIP4P/2005。还计算了纯液态水的压力对自扩散系数和剪切黏度的影响,这些性质的异常行为得到了定性的很好预测。此外,基于 SPC/E 和 TIP4P/2005 水模型,计算了包含甲醇或乙醇的水二元混合物的输运性质以及过剩体积和过剩焓。在所测试的条件下,TIP4P/2005 模型对所研究的输运性质给出了与实验最好的定量和定性一致。对于纯液态水,实验数据的偏差为 5%至 15%,对于水+醇混合物,偏差为 5%至 20%。此外,还分析了水以及所研究混合物的质心功率谱,并讨论了不同状态下的氢键结构。

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