Yang Jie, Kondrat Svyatoslav, Lian Cheng, Liu Honglai, Schlaich Alexander, Holm Christian
Institute for Computational Physics, University of Stuttgart, 70569 Stuttgart, Germany.
School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.
Phys Rev Lett. 2023 Sep 15;131(11):118201. doi: 10.1103/PhysRevLett.131.118201.
Using classical density functional theory, we investigate the influence of solvent on the structure and ionic screening of electrolytes under slit confinement and in contact with a reservoir. We consider a symmetric electrolyte with implicit and explicit solvent models and find that spatially resolving solvent molecules is essential for the ion structure at confining walls, excess ion adsorption, and the pressure exerted on the walls. Despite this, we observe only moderate differences in the period of oscillations of the pressure with the slit width and virtually coinciding decay lengths as functions of the scaling variable σ_{ion}/λ_{D}, where σ_{ion} is the ion diameter and λ_{D} the Debye length. Moreover, in the electrostatic-dominated regime, this scaling behavior is practically independent of the relative permittivity and its dependence on the ion concentration. In contrast, the crossover to the hard-core-dominated regime depends sensitively on all three factors.
利用经典密度泛函理论，我们研究了溶剂对狭缝限制下且与储液器接触的电解质的结构和离子屏蔽的影响。我们考虑了具有隐式和显式溶剂模型的对称电解质，发现对溶剂分子进行空间分辨对于限制壁处的离子结构、过量离子吸附以及施加在壁上的压力至关重要。尽管如此，我们观察到压力随狭缝宽度的振荡周期只有适度差异，并且作为缩放变量σ_{ion}/λ_{D}的函数，衰减长度几乎重合，其中σ_{ion}是离子直径，λ_{D}是德拜长度。此外，在静电主导区域，这种缩放行为实际上与相对介电常数及其对离子浓度的依赖性无关。相比之下，向硬核主导区域的转变敏感地取决于所有这三个因素。
