Patra Chandra N
Theoretical Chemistry Section, Chemistry Group, Bhabha Atomic Research Centre Mumbai 400 085 India.
RSC Adv. 2020 Oct 23;10(64):39017-39025. doi: 10.1039/d0ra06145j. eCollection 2020 Oct 21.
Size and charge correlations in spherical electric double layers are investigated through Monte Carlo simulations and density functional theory, through a solvent primitive model representation. A fully asymmetric mixed electrolyte is used for the small ions, whereas the solvent, apart from being a continuum dielectric, is also treated as an individual component. A partially perturbative density functional theory is adopted here, and for comparison, a standard canonical ensemble Monte Carlo simulation is used. The hard-sphere free energy is treated within a weighted density approach and the residual ionic contribution is estimated through perturbation around the uniform density. The results from both methods corroborate each other quantitatively over a wide range of physical parameters. The importance of structural correlations is envisaged through the size and charge asymmetry of the supporting electrolytes that includes the solvent as a component.
通过蒙特卡罗模拟和密度泛函理论，借助溶剂原胞模型表示法，研究了球形双电层中的尺寸与电荷相关性。小离子采用完全不对称的混合电解质，而溶剂除了作为连续介质外，还被视为单独的组分。这里采用部分微扰密度泛函理论，作为比较，还使用了标准正则系综蒙特卡罗模拟。硬球自由能采用加权密度方法处理，残余离子贡献通过围绕均匀密度的微扰来估计。两种方法的结果在广泛的物理参数范围内相互定量印证。通过包含溶剂作为组分的支持电解质的尺寸和电荷不对称性，设想了结构相关性的重要性。
