Henderson D, Bryk P, Sokołowski S, Wasan D T
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602-5700, USA.
Phys Rev E Stat Phys Plasmas Fluids Relat Interdiscip Topics. 2000 Apr;61(4 Pt A):3896-903. doi: 10.1103/physreve.61.3896.
Results are reported for the primitive model of an electrolyte and for the solvent primitive model of an electrolyte for the case where these fluids are confined by two charged walls. When the walls are thin, the confined electrolyte inside the walls is affected by the charge on both the inside and the outside of the walls. In the case of the primitive model (PM), this system has been studied previously using a singlet integral equation. Our density-functional (DF) study is more general because the fluids inside and outside the walls are constrained to have the same chemical potential and because solvent effects are considered, albeit at a crude level. The singlet integral equation does not consider the chemical potential constraint explicitly. We find that for the low density PM, the DF and integral equation approaches yield, except for a very narrow pore, very similar results. When solvent molecules are considered, the profiles become oscillatory. The co-ion density profiles are particularily interesting because the repulsive electrostatic potential and the effect of the increased pressure in "pushing" the co-ions against the wall compete.
报告了电解质的原始模型以及电解质的溶剂原始模型在被两个带电壁限制情况下的结果。当壁很薄时，壁内受限的电解质会受到壁内外电荷的影响。在原始模型（PM）的情况下，该系统先前已使用单重积分方程进行过研究。我们的密度泛函（DF）研究更具普遍性，因为壁内外的流体被约束具有相同的化学势，并且考虑了溶剂效应，尽管是在粗略的层面上。单重积分方程没有明确考虑化学势约束。我们发现，对于低密度的PM，除了非常窄的孔隙外，DF方法和积分方程方法得出的结果非常相似。当考虑溶剂分子时，分布曲线会出现振荡。同离子密度分布曲线特别有趣，因为排斥性静电势和“推动”同离子靠向壁的压力增加的效应相互竞争。
