Center for Micro-Engineered Materials and Department of Chemical and Biological Engineering, University of New Mexico, Albuquerque, New Mexico 87131, USA.
J Chem Phys. 2017 Dec 7;147(21):214704. doi: 10.1063/1.5005060.
Electric double layers are complex systems that involve a wide variety of interactions between the different components of the electrolyte solutions and with the charged interface. While the role of all Coulombic types of interactions is clear, that of the non-Coulombic forces is less obvious. The focus in the present study is on the effect of bulk solvation interactions on the properties of the electric double layer. The analysis is based on classical density functional theory. This approach allows us to account for the correlations between all charged (ionic) and uncharged (solvent) species in the solution. The surface charge at the boundary of the electric double layer is derived from the surface chemistry pertinent to the system. The surface is sensitive to the concentration of potential determining ions, which in turn depends on the correlations and activities of all remaining components. The analysis shows that the solvation forces have a profound effect on the charge and potential distributions in an electric double layer. This is true not just for the solvation of the potential determining ions, but for all species. Even varying the solvent-solvent interaction has a significant impact on the charge and potential distributions in the electric double layer.
双电层是一个复杂的系统，涉及电解质溶液的不同成分之间以及与带电界面之间的各种相互作用。虽然所有库仑类型相互作用的作用是明确的，但非库仑力的作用则不那么明显。本研究的重点是体相溶剂化相互作用对双电层性质的影响。分析基于经典密度泛函理论。这种方法使我们能够考虑溶液中所有带电（离子）和不带电（溶剂）物种之间的相关性。双电层边界处的表面电荷来自于与系统相关的表面化学。表面对决定电位离子的浓度很敏感，而离子的浓度又取决于所有剩余成分的相关性和活度。分析表明，溶剂化力对双电层中的电荷和电势分布有深远的影响。这不仅适用于决定电位离子的溶剂化，也适用于所有物种。即使改变溶剂-溶剂相互作用，也会对双电层中的电荷和电势分布产生重大影响。
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