Patra Chandra N
Theoretical Chemistry Section, Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085, India.
J Chem Phys. 2014 Nov 14;141(18):184702. doi: 10.1063/1.4901217.
A systematic investigation of the spherical electric double layers with the electrolytes having size as well as charge asymmetry is carried out using density functional theory and Monte Carlo simulations. The system is considered within the primitive model, where the macroion is a structureless hard spherical colloid, the small ions as charged hard spheres of different size, and the solvent is represented as a dielectric continuum. The present theory approximates the hard sphere part of the one particle correlation function using a weighted density approach whereas a perturbation expansion around the uniform fluid is applied to evaluate the ionic contribution. The theory is in quantitative agreement with Monte Carlo simulation for the density and the mean electrostatic potential profiles over a wide range of electrolyte concentrations, surface charge densities, valence of small ions, and macroion sizes. The theory provides distinctive evidence of charge and size correlations within the electrode-electrolyte interface in spherical geometry.
利用密度泛函理论和蒙特卡罗模拟，对具有尺寸和电荷不对称性的电解质的球形双电层进行了系统研究。该系统在原始模型中进行考虑，其中大离子是无结构的硬球形胶体，小离子是不同尺寸的带电硬球，溶剂表示为介电连续体。本理论使用加权密度方法近似单粒子关联函数的硬球部分，而围绕均匀流体进行微扰展开以评估离子贡献。该理论在广泛的电解质浓度、表面电荷密度、小离子价态和大离子尺寸范围内，与密度和平均静电势分布的蒙特卡罗模拟结果在定量上一致。该理论为球形几何结构中电极 - 电解质界面内的电荷和尺寸相关性提供了独特的证据。
