Laboratoire des Fluides Complexes et leurs Réservoirs, UMR5150, Université de Pau et des Pays de L'Adour, B.P. 1155, Pau, Cedex 64013, France.
J Phys Chem B. 2011 Aug 11;115(31):9618-25. doi: 10.1021/jp202276k. Epub 2011 Jul 15.
This work is dedicated to the simultaneous application of the gradient theory of fluid interfaces and Monte Carlo molecular simulations for the description of the interfacial behavior of the methane/water mixture. Macroscopic (interfacial tension, adsorption) and microscopic (density profiles, interfacial thickness) properties are investigated. The gradient theory is coupled in this work with the SAFT-VR Mie equation of state. The results obtained are compared with Monte Carlo simulations, where the fluid interface is explicitly considered in biphasic simulation boxes at both constant pressure and volume (NPT and NVT ensembles), using reliable united atom molecular models. On one hand, both methods provide very good estimations of the interfacial tension of this mixture over a broad range of thermodynamic conditions. On the other hand, microscopic properties computed with both gradient theory and MC simulations are in very good agreement with each other, which confirms the consistency of both approaches. Interfacial tension minima at high pressure and prewetting transitions in the vicinity of saturation conditions are also investigated.
这项工作致力于同时应用流体界面的梯度理论和蒙特卡罗分子模拟来描述甲烷/水混合物的界面行为。研究了宏观（界面张力、吸附）和微观（密度分布、界面厚度）性质。在这项工作中，梯度理论与 SAFT-VR Mie 状态方程耦合。将得到的结果与蒙特卡罗模拟进行了比较，其中在恒压和恒容（NPT 和 NVT 系综）条件下，在两相模拟盒中显式地考虑了流体界面，使用可靠的统一原子分子模型。一方面，这两种方法都能很好地估算该混合物在很宽的热力学条件范围内的界面张力。另一方面，用梯度理论和 MC 模拟计算得到的微观性质彼此非常吻合，这证实了两种方法的一致性。还研究了高压下的界面张力最小值和接近饱和条件下的预湿转变。
