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硬球的热力学压力和封闭维里状态方程。

Thermodynamic pressures for hard spheres and closed-virial equation-of-state.

机构信息

School of Chemical Engineering and Analytical Science, The University of Manchester, P.O. Box 88, Sackville Street, Manchester M60 1QD, United Kingdom.

出版信息

J Chem Phys. 2010 Feb 28;132(8):084507. doi: 10.1063/1.3328823.

Abstract

Hard-sphere molecular dynamics (MD) simulation results, with six-figure accuracy in the thermodynamic equilibrium pressure, are reported and used to test a closed-virial equation-of-state. This latest equation, with no adjustable parameters except known virial coefficients, is comparable in accuracy both to Padé approximants, and to numerical parameterizations of MD data. There is no evidence of nonconvergence at stable fluid densities. The virial pressure begins to deviate significantly from the thermodynamic fluid pressure at or near the freezing density, suggesting that the passage from stable fluid to metastable fluid is associated with a higher-order phase transition; an observation consistent with some previous experimental results. Revised parameters for the crystal equation-of-state [R. J. Speedy, J. Phys.: Condens. Matter 10, 4387 (1998)] are also reported.

摘要

硬球分子动力学(MD)模拟结果具有热力学平衡压力的六位数精度,用于测试封闭维里状态方程。这个最新的方程,除了已知的维里系数外,没有可调参数,在准确性上可与 Padé 逼近和 MD 数据的数值参数化相媲美。在稳定的流体密度下,没有出现不收敛的迹象。维里压力在冻结密度或接近冻结密度时开始显著偏离热力学流体压力,这表明从稳定流体到亚稳流体的转变与高阶相变有关;这一观察结果与一些先前的实验结果一致。还报告了晶体状态方程的修订参数[R. J. Speedy,J. Phys.:Condens. Matter 10, 4387(1998)]。

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