Thermodynamic functions as correlation-function integrals.
Thermodynamic functions as correlation-function integrals.
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热力学函数作为相关函数积分。
DOI：
10.1063/1.4795498
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
B. Widom
中科院分区：
文献类型：
--
作者：
Kenichiro Koga;B. Widom
回顾了一些热力学函数的相关函数积分表达式，如Ornstein-Zernike积分、Kirkwood-Buff积分和维里系数的积分公式。注意，如前所述，测量分子间距离的分子中心的选择是任意的，不同的选择导致不同形式的相关函数，但积分必须与这些选择无关。这是说明与第二维里系数的硬球在一个，两个和三个维度，与气态丙烷在三个维度，并与计算机模拟的对相关性在水中和在丙烷的稀水溶液。
Expressions of some thermodynamic functions as correlation-function integrals, such as the Ornstein-Zernike integral, the Kirkwood-Buff integrals, and the integral formulas for virial coefficients, are recalled. It is noted, as has been remarked before, that the choice of molecular centers from which intermolecular distances are measured is arbitrary and that different choices lead to different forms of the correlation functions but that the integrals must be independent of those choices. This is illustrated with the second virial coefficients of hard spheres in one, two, and three dimensions, with that of gaseous propane in three dimensions, and with computer simulations of the pair correlations in water and in a dilute aqueous solution of propane.