Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India.
J Chem Phys. 2010 Apr 14;132(14):144501. doi: 10.1063/1.3382345.
Prewetting transitions are studied for Lennard-Jones (LJ) based dimer forming associating fluids, on a structureless surface represented by LJ 9-3 type potential, for various association strengths using grand-canonical transition matrix Monte Carlo (GC-TMMC) and histogram reweighting techniques. Occurrences of prewetting transition are observed for association strengths: epsilon(af)=2.0, 4.0, 6.0, 8.0, and 10.0. Structural properties, monomer fraction, and orientation order profile of thin-thick film of one-site associating fluids are presented. Wetting temperature, T(w), and prewetting critical temperature, T(pwc), increases with increasing association strength, which is in agreement with the results of the density functional theory (DFT). Length of prewetting line, on the other hand, is found to decrease first with increasing association energy until epsilon(af)=8.0 and subsequently found to increase substantially for epsilon(af)=10. This behavior is contrary to the prediction from the DFT. We observe that the boundary tension of thin-thick film via GC-TMMC and finite size scaling exhibits a maximum with respect to association strength.
在由 LJ9-3 型势能表示的无结构表面上,我们使用巨正则转换矩阵蒙特卡罗 (GC-TMMC) 和直方图再加权技术,研究了各种关联强度下 Lennard-Jones (LJ) 基二聚体形成缔合流体的预润湿转变。在关联强度为 epsilon(af)=2.0、4.0、6.0、8.0 和 10.0 时,观察到预润湿转变的发生。我们提出了单站点缔合流体的薄厚膜的结构特性、单体分数和取向序分布。与密度泛函理论 (DFT) 的结果一致,润湿温度 T(w) 和预润湿临界温度 T(pwc) 随着关联强度的增加而增加。另一方面,预润湿线的长度发现,在 epsilon(af)=8.0 之前,随着关联能的增加而先减小,然后在 epsilon(af)=10.0 时显著增加。这种行为与 DFT 的预测相反。我们观察到,通过 GC-TMMC 和有限尺寸标度,薄厚膜的边界张力表现出与关联强度的最大值。