Optimized perturbed hard sphere expressions for the structure and thermodynamics of Lennard-Jones fluids
Optimized perturbed hard sphere expressions for the structure and thermodynamics of Lennard-Jones fluids
复制标题
Lennard-Jones 流体结构和热力学的优化扰动硬球表达式
DOI：
10.1080/00268979300100131
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发表时间：
1993
影响因子：
1.7
通讯作者：
D. Ben‐Amotz
中科院分区：
文献类型：
--
作者：
Luís E. S. de Souza;D. Ben‐Amotz
以两个Lennard-Jones常数为可调参数，用Lennard-Jones流体压缩因子Z和内能U数据对一阶扰动硬球流体表达式进行了拟合。结果被用来区分在广泛的密度和温度范围内替代微扰算法的实用性。一阶Barker-Henderson微扰表达式系统地低估了热力学性质随温度的变化，而Week-Chandler-Andersen模型被发现能合理地重现整个液体和超临界流体领域的模拟结果，有效Lennard-Jones参数只有几个百分点的调整。给出了Barker-Henderson和Week-Chandler-Andersen硬球直径的封闭解析表达式以及硬流体参照系的径向分布函数模型。结果表明，这些结果能够准确地再现Lennard-Jones的硬球直径和热力学性质。
First-order perturbed hard sphere fluid expressions are fitted to Lennard-Jones fluid compressibility factor, Z, and internal energy, U, data taking the two Lennard-Jones constants as adjustable parameters. The results are used to distinguish the utility of alternative perturbative algorithms over a wide density and temperature range. First-order Barker-Henderson perturbative expressions are found to systematically underestimate temperature dependent changes in thermodynamic properties while the Weeks-Chandler-Andersen model is found to reasonably reproduce simulation results throughout the liquid and supercritical fluid domain, with only a few per cent adjustment of the effective Lennard-Jones parameters. Closed analytical expressions for the Barker-Henderson and Weeks-Chandler-Andersen hard sphere diameters as well as a hard fluid reference system radial distribution function model are presented. These are shown to accurately reproduce hard sphere diameters and thermodynamic properties of Lennard-Jones ...