Wang Rui, Wang Zhen-Gang
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
J Chem Phys. 2016 Apr 7;144(13):134902. doi: 10.1063/1.4945011.
Screening is one of the most important concepts in the study of charged systems. Near a dielectric interface, the ion distribution in a salt solution can be highly nonuniform. Here, we develop a theory that self-consistently treats the inhomogeneous screening effects. At higher concentrations when the bulk Debye screening length is comparable to the Bjerrum length, the double layer structure and interfacial properties are significantly affected by the inhomogeneous screening. In particular, the depletion zone is considerably wider than that predicted by the bulk screening approximation or the WKB approximation. The characteristic length of the depletion layer in this regime scales with the Bjerrum length, resulting in a linear increase of the negative adsorption of ions with concentration, in agreement with experiments. For asymmetric salts, inhomogeneous screening leads to enhanced charge separation and surface potential.
筛选是带电系统研究中最重要的概念之一。在介电界面附近,盐溶液中的离子分布可能高度不均匀。在此,我们发展了一种自洽处理非均匀筛选效应的理论。在较高浓度下,当本体德拜筛选长度与 Bjerrum 长度相当时,双层结构和界面性质会受到非均匀筛选的显著影响。特别是,耗尽区比本体筛选近似或 WKB 近似所预测的要宽得多。在这种情况下,耗尽层的特征长度与 Bjerrum 长度成比例,导致离子的负吸附随浓度呈线性增加,这与实验结果一致。对于不对称盐,非均匀筛选会导致电荷分离增强和表面电势增加。