Entropy in Molecular Fluids: Interplay between Interaction Complexity and Criticality
Entropy in Molecular Fluids: Interplay between Interaction Complexity and Criticality
复制标题
分子流体中的熵：相互作用复杂性和临界性之间的相互作用
DOI：
10.1021/acs.jpcb.0c08014
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Delhommelle, Jerome
中科院分区：
文献类型：
--
作者：
Desgranges, Caroline;Delhommelle, Jerome
使用平坦直方图模拟，我们计算了分子流体沿着气液相边界的熵。我们的模拟方法是基于正则和巨正则配分函数的评估，这反过来又提供了通过统计力学形式主义的熵。结果使我们能够确定临界熵的分子流体，并揭示过渡发生对称的熵的观点。这可以通过热力学变量温度和压力相对于共存相的熵绘制时所表现出的模式最好地看出。这种行为被发现持有非极性，四极，和偶极流体。最后，我们确定功能的形式，表征热力学变量和熵之间的关系沿着共存曲线的临界点。
Using flat-histogram simulations, we calculate the entropy of molecular fluids along the vapor–liquid phase boundary. Our simulation approach is based on the evaluation of the canonical and grand-canonical partition functions, which, in turn, provide access to entropy through the statistical mechanics formalism. The results allow us to determine the critical entropy of molecular fluids and to uncover that the transition occurs symmetrically from an entropic standpoint. This can best be seen through the patterns exhibited by the thermodynamic variables temperature and pressure when plotted against the entropy of the coexisting phases. This behavior is found to hold for apolar, quadrupolar, and dipolar fluids. Finally, we identify functional forms that characterize the relation between thermodynamic variables and entropy along the coexistence curve up to the critical point.