Abstract The Lennard-Jones (LJ) potential is widely used for describing simple fluids; it is also a point of departure for developing models of complex fluids. Thermodynamic properties of the LJ fluid have been studied by molecular simulations by many authors and a critical review of the available data, which comprises about 35,000 data points, has been published recently [J. Chem. Inf. Mod. 59 (2019) 4248–4265]. The importance of the LJ fluid has also triggered the development of a large number of equations of state (EOS). In the present work, 20 LJ EOS were critically assessed by comparing their results with consolidated data from computer experiments. A large variety of thermophysical properties was considered: vapor pressure; saturated densities; enthalpy of vaporization; critical properties; thermal, caloric, and entropic properties at homogeneous state points; and second and third virial coefficients. It was found that none of the available LJ EOS meets the following two criteria: (1) it does not yield unphysical artifacts when used for extrapolations, and (2) it describes data from computer experiments within their statistical uncertainty in most fluid regions. Furthermore, a re-parameterization of the monomer term of the PC-SAFT EOS was carried out by fitting it to data of the LJ fluid. The new LJ EOS yields good results for the LJ fluid, but does not outperform the best existing LJ EOS.

中文翻译：

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Lennard-Jones 流体状态方程的回顾与比较

摘要 Lennard-Jones (LJ) 势被广泛用于描述简单流体。它也是开发复杂流体模型的起点。许多作者已经通过分子模拟研究了 LJ 流体的热力学特性，最近发表了对可用数据的批判性评论，其中包括大约 35,000 个数据点 [J. 化学 信息 国防部。59 (2019) 4248–4265]。LJ 流体的重要性也引发了大量状态方程 (EOS) 的发展。在目前的工作中，通过将其结果与计算机实验的综合数据进行比较，对 20 LJ EOS 进行了严格评估。考虑了多种热物理特性：蒸气压；饱和密度；汽化焓；关键属性；热量，热量，和均匀状态点的熵特性；以及第二和第三维里系数。发现所有可用的 LJ EOS 都不符合以下两个标准：(1) 在用于外推时不会产生非物理伪影，以及 (2) 它描述了大多数流体区域中计算机实验的统计不确定性内的数据。此外，通过将 PC-SAFT EOS 的单体项拟合到 LJ 流体的数据，对其进行了重新参数化。新的 LJ EOS 对 LJ 流体产生了良好的结果，但没有优于现有的最佳 LJ EOS。(2) 它描述了大多数流体区域中计算机实验的统计不确定性内的数据。此外，通过将 PC-SAFT EOS 的单体项拟合到 LJ 流体的数据，对其进行了重新参数化。新的 LJ EOS 对 LJ 流体产生了良好的结果，但没有优于现有的最佳 LJ EOS。(2) 它描述了在大多数流体区域的统计不确定性范围内的计算机实验数据。此外，通过将 PC-SAFT EOS 的单体项拟合到 LJ 流体的数据，对其进行了重新参数化。新的 LJ EOS 对 LJ 流体产生了良好的结果，但没有优于现有的最佳 LJ EOS。