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在 Ne 填充平面狭缝时的非对称轮廓和预湿线。

Asymmetric profiles and prewetting lines in the filling of planar slits with Ne.

机构信息

Instituto de Desarrollo Humano, Universidad Nacional de General Sarmiento, Gutierrez 1150, RA-1663 San Miguel, Argentina.

出版信息

J Phys Chem B. 2013 May 23;117(20):6256-68. doi: 10.1021/jp4000895. Epub 2013 May 14.

Abstract

The filling of slits with identical planar walls is investigated in the frame of the density functional theory. For this kind of slit, the confining potential is symmetric with respect to its central plane. Closed and open systems are studied by applying, respectively, the canonical and grand canonical ensembles (CE and GCE). Results obtained for the confinement of fluid Ne by alkaline surfaces are reported. The behavior of these systems is analyzed by varying the strength of the Ne-substrate attraction, the temperature T, and the coverage Γ(l). It is assumed that the one-body density of the fluid, ρ(r), is uniform along the (x, y) planes parallel to the walls, becoming a function of the coordinate z perpendicular to those planes. Two sorts of solutions are found for the density profile: (i) symmetric ones that follow the left-right symmetry of the potential exerted by the walls and (ii) asymmetric ones that break the symmetry of the slit. The pores are wide enough for determining prewetting (PW) lines and wetting and critical PW temperatures, i.e., T(w) and T(cpw), from the analysis of symmetric solutions provided by both the CE and GCE schemes. Asymmetric species are examined in detail for T > T(w). It is shown that for a given Ne-substrate pair at a fixed T both the CE and GCE frames yield only one asymmetric 2-fold degenerate stable profile (formed by a "thin" wetting film at one wall and a "thick" wetting film at the other) coexisting with two symmetric profiles (formed by "thin" or "thick" wetting films at the two walls), while the remaining asymmetric states are at best metastable. This feature occurs along PW lines and disappears at T(cpw).

摘要

本文在密度泛函理论的框架下研究了具有相同平面壁的狭缝的填充。对于这种狭缝,约束势相对于其中心平面是对称的。通过分别应用正则系综(CE)和巨正则系综(GCE)研究了封闭系统和开放系统。报道了用碱性表面约束流体 Ne 的结果。通过改变 Ne-衬底吸引的强度、温度 T 和覆盖度 Γ(l),分析了这些系统的行为。假设流体的单个体密度 ρ(r) 在与壁平行的 (x, y) 平面上是均匀的,而在垂直于这些平面的坐标 z 上则是一个函数。对于密度分布,找到了两种类型的解:(i)对称解,它们遵循壁施加的势的左右对称;(ii)非对称解,它们打破了狭缝的对称。对于较宽的孔隙,可以通过分析 CE 和 GCE 方案提供的对称解来确定预润湿(PW)线以及润湿和临界 PW 温度,即 T(w)和 T(cpw)。对于 T > T(w),详细研究了非对称物种。结果表明,对于给定的 Ne-衬底对在固定 T 下,CE 和 GCE 框架都只给出一个非对称的 2 重简并稳定分布(由一个壁上的“薄”润湿膜和另一个壁上的“厚”润湿膜形成),与两个对称分布(由两个壁上的“薄”或“厚”润湿膜形成)共存,而其余的非对称状态最多是亚稳态。这一特征出现在 PW 线上,并在 T(cpw) 处消失。

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