Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
J Chem Phys. 2010 May 28;132(20):204702. doi: 10.1063/1.3428704.
We use classical density functional theory (DFT) and an explicit solvent description to investigate the wetting and drying behavior of ionic solutions in contact with a charged solid substrate. The solvent is modeled by dipolar hard spheres, while the monovalent ions are oppositely charged hard spheres; cohesion is ensured by a Yukawa attraction between all three species. The free energy functional describing the inhomogeneous solution includes the best available fundamental measure description of excluded volume correlations in a ternary mixture of hard spheres, whereas all electrostatic and cohesive interactions are treated within the mean-field approximation. We find both first and second order wetting transitions which are rather little affected by ions at low and moderate concentrations, compared to the wetting behavior of the pure solvent. A novel drying scenario is predicted, where complete drying is prevented by the electrostatic attraction between a positively charged substrate and the anions, while near a negatively charged substrate, a first order transition with a predrying line is observed. The various scenarios are surprisingly similar to our previous predictions based on a "semiprimitive" model where the solvent particles carry no dipole, but the ion-ion interactions are reduced by a local dielectric permittivity.
我们使用经典密度泛函理论(DFT)和显式溶剂描述来研究带电荷的固体基底接触的离子溶液的润湿和干燥行为。溶剂由偶极硬球模拟,单价离子为带相反电荷的硬球;通过所有三种物质之间的 Yukawa 吸引力确保内聚。描述不均匀溶液的自由能泛函包括三元硬球混合物中排除体积相关的最佳基本测量描述,而所有静电和内聚相互作用都在平均场近似中处理。我们发现了一级和二级润湿转变,与纯溶剂的润湿行为相比,在低浓度和中等浓度下,离子的影响相当小。预测了一种新的干燥情况,带正电荷的基底和阴离子之间的静电吸引力阻止了完全干燥,而在带负电荷的基底附近,则观察到具有预干燥线的一级转变。各种情况与我们之前基于“半原始”模型的预测非常相似,其中溶剂颗粒不带偶极子,但通过局部介电常数减小了离子-离子相互作用。