尺寸不对称电解质球形双电层的模拟和理论研究：大共离子情况
A simulational and theoretical study of the spherical electrical double layer for a size-asymmetric electrolyte: the case of big coions
摘要：
在原始模型中，对被尺寸不对称电解质包围的球形大离子进行了蒙特卡罗模拟。我们考虑了尺寸比为2的1：1和2：2盐（即，具有抗衡离子尺寸的两倍的共离子），对于大球体的几个表面电荷密度。的径向分布函数，在亥姆霍兹表面的静电势，和综合电荷的报告。我们将这些模拟数据与从Ornstein-Zernike积分方程获得的原始结果进行比较，并补充了超网链/超网链（HNC/HNC）和超网链/平均球面近似（HNC/MSA）闭包，以及使用修改的Gouy-Chapman和不等半径修改的Gouy-Chapman理论进行相应的计算。HNC/HNC和HNC/MSA积分方程形式主义显示出良好的一致性与Monte Carlo“实验”，而点离子方法的显着局限性是显而易见的。最重要的是，模拟证实了我们以前的理论预测的反离子在尺寸不对称的球形双电层[J. Chem. Phys. 123，034703（2005）]，在外部亥姆霍兹平面的异常曲率的外观和电荷反转的增强和筛选高胶体表面电荷密度由于离子尺寸不对称。
英文摘要：
Monte Carlo simulations of a spherical macroion, surrounded by a size-asymmetric electrolyte in the primitive model, were performed. We considered 1:1 and 2:2 salts with a size ratio of 2 (i.e., with coions twice the size of counterions), for several surface charge densities of the macrosphere. The radial distribution functions, electrostatic potential at the Helmholtz surfaces, and integrated charge are reported. We compare these simulational data with original results obtained from the Ornstein-Zernike integral equation, supplemented by the hypernetted chain/hypernetted chain (HNC/HNC) and hypernetted chain/mean spherical approximation (HNC/MSA) closures, and with the corresponding calculations using the modified Gouy-Chapman and unequal-radius modified Gouy-Chapman theories. The HNC/HNC and HNC/MSA integral equations formalisms show good concordance with Monte Carlo "experiments", whereas the notable limitations of point-ion approaches are evidenced. Most importantly, the simulations confirm our previous theoretical predictions of the non-dominance of the counterions in the size-asymmetric spherical electrical double layer [J. Chem. Phys. 123, 034703 (2005)], the appearance of anomalous curvatures at the outer Helmholtz plane and the enhancement of charge reversal and screening at high colloidal surface charge densities due to the ionic size asymmetry.
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