Amabili M, Meloni S, Giacomello A, Casciola C M
Dipartimento di Ingegneria Meccanica e Aerospaziale, Università di Roma "La Sapienza" , 00184 Rome, Italy.
J Phys Chem B. 2018 Jan 11;122(1):200-212. doi: 10.1021/acs.jpcb.7b07429. Epub 2017 Dec 28.
A liquid in contact with a textured surface can be found in two states, Wenzel and Cassie. In the Wenzel state the liquid completely wets the corrugations while in the Cassie state the liquid is suspended over the corrugations with air or vapor trapped below. The superhydrophobic properties of the Cassie state are exploited for self-cleaning, drag reduction, drug delivery, etc., while in the Wenzel state most of these properties are lost; it is therefore of great fundamental and technological interest to investigate the kinetics and mechanism of the Cassie-Wenzel transition. Computationally, the Cassie-Wenzel transition is often investigated using enhanced sampling ("rare events") techniques based on the use of collective variables (CVs). The choice of the CVs is a crucial task because it affects the free-energy profile, the estimation of the free-energy barriers, and the evaluation of the mechanism of the process. Here we investigate possible simulation artifacts introduced by common CVs adopted for the study of the Cassie-Wenzel transition: the average particle density in the corrugation of a textured surface and the coarse-grained density field at various levels of coarse graining. We also investigate possible additional artifacts associated with finite size effects. We focus on a pillared surface, a system often used in technological applications. We show that the use of a highly coarse-grained density (a single CV) of the fluid in the interpillar region brings to severe artifacts: errors of hundreds of kT in the difference of free energy between the Cassie and Wenzel states, of tens of kT in the estimate of the free-energy barriers, and erroneous wetting mechanisms. A proper description of the wetting mechanism and its energetics apparently requires a fine discretization of the density field. Concerning the finite-size effects, we have found that the typical systems employed in simulations of the Cassie-Wenzel transition, containing a single pillar within periodic boundary conditions, prevent the complete break of translational symmetry of the liquid-vapor meniscus during the process. Capturing this break of symmetry is crucial for describing the transition state along the wetting process and the early stage of the opposite process, the Wenzel-Cassie transition.
文策尔(Wenzel)状态和卡西(Cassie)状态。在文策尔状态下,液体完全润湿波纹,而在卡西状态下,液体悬浮在波纹上方,空气或蒸汽被困在下方。卡西状态的超疏水特性被用于自清洁、减阻、药物递送等方面,而在文策尔状态下,这些特性大多会丧失;因此,研究卡西 - 文策尔转变的动力学和机制具有重大的基础和技术意义。在计算方面,卡西 - 文策尔转变通常使用基于集体变量(CVs)的增强采样(“稀有事件”)技术进行研究。集体变量的选择是一项关键任务,因为它会影响自由能分布、自由能垒的估计以及过程机制的评估。在此,我们研究了用于卡西 - 文策尔转变研究的常见集体变量引入的可能模拟伪像:有纹理表面波纹中的平均粒子密度以及不同粗粒化水平下的粗粒化密度场。我们还研究了与有限尺寸效应相关的可能额外伪像。我们聚焦于柱状表面,这是一种常用于技术应用的系统。我们表明,在柱间区域使用流体的高度粗粒化密度(单个集体变量)会带来严重伪像:卡西状态和文策尔状态之间自由能差的误差达数百kT,自由能垒估计误差达数十kT,以及错误的润湿机制。对润湿机制及其能量学的恰当描述显然需要对密度场进行精细离散化。关于有限尺寸效应,我们发现,在卡西 - 文策尔转变模拟中使用的典型系统,即在周期性边界条件下包含单个柱子的系统,会阻止液体 - 蒸汽弯月面在过程中完全打破平移对称性。捕捉这种对称性破缺对于描述沿润湿过程的过渡态以及相反过程(文策尔 - 卡西转变)的早期阶段至关重要。