从关于不对称电解质混合物中平面电双层电荷反转的蒙特卡罗模拟中得到的见解。
Insights from Monte Carlo simulations on charge inversion of planar electric double layers in mixtures of asymmetric electrolytes.
机构信息
Department of Physics and National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, China.
出版信息
J Chem Phys. 2010 Aug 14;133(6):064704. doi: 10.1063/1.3469795.
Monte Carlo simulations of a planar negatively charged dielectric interface in contact with a mixture of 1:1 and 3:1 electrolytes are carried out using the unrestricted primitive model under more realistic hydrated ion sizes. Two typical surface charge densities are chosen to represent the systems from the weak to strong coupling regimes. Our goal is to determine the dependence of the degree of charge inversion on increasing concentration of both mono- and trivalent salts and to provide a systematic study on this peculiar effect between short-range and electrostatic correlations. The numerical results show that addition of monovalent salt diminishes the condensation of trivalent counterions due to either the favorable solvation energy or the available space constraints. As the concentration of trivalent salt increases, on the other hand, the inclusion of the ionic size and size asymmetry results in a damped oscillatory charge inversion at low enough surface charge and another counterintuitive surface charge amplification. It is proposed that both of the anomalous events in the weak coupling regime are thought to be entropic in origin which is completely different from the electrostatic driven charge inversion in the strong coupling regime. In addition, the electrostatic images arising from the dielectric mismatch lead to a decaying depletion effect on the structure of double layer with growing salt concentration in the case of low charged interface but have no effect at high surface charge values. The microscopic information obtained here points to the need for a more quantitative theoretical treatment in describing the charge inversion phenomenon of real colloidal systems.
采用无限制原始模型,对与 1:1 和 3:1 电解质混合物接触的平面带负电荷介电界面进行了蒙特卡罗模拟,考虑了更实际的水合离子尺寸。选择了两种典型的表面电荷密度来代表从弱耦合到强耦合体系的系统。我们的目标是确定增加单价和单价盐浓度对电荷反转程度的依赖性,并对短程和静电相关性之间的这种特殊效应进行系统研究。数值结果表明,由于有利的溶剂化能或可用空间限制,单价盐的添加减少了单价抗衡离子的凝聚。另一方面,随着三价盐浓度的增加,离子尺寸和尺寸不对称性的包含导致在足够低的表面电荷下,电荷反转呈阻尼振荡,以及另一种反直觉的表面电荷放大。据提出,弱耦合区的两种异常现象都被认为是熵驱动的,这与强耦合区的静电驱动电荷反转完全不同。此外,由于介电失配产生的静电图像导致在低电荷界面的情况下,随着盐浓度的增加,双层结构的耗尽效应逐渐衰减,但在高表面电荷值时没有影响。这里获得的微观信息表明,需要更定量的理论处理来描述实际胶体系统的电荷反转现象。