The effect of multivalent counterions on the spherical electric double layers containing asymmetric electrolytes with size and charge asymmetry is studied using density functional theory and Monte Carlo simulations, in a systematic manner. A primitive model representation of the system is followed, where the macroion and small ions are represented as uniformly charged hard spheres of different size within a dielectric continuum as solvent. The theory approximates the hard-sphere contribution through a weighted density approach, whereas a functional expansion around the uniform fluid is used for the ionic part. The theory reproduces the simulation data quantitatively for a wide range of system parameters. The present study reflects the importance of size and charge correlations with inclusion of multivalent counterions as observed in spherical double layers.

运用密度泛函理论和蒙特卡洛模拟，系统地研究了多价抗衡离子对球形非电对称双电层的影响，该双电层包含尺寸和电荷不对称的不对称电解质。遵循该系统的原始模型表示，其中大分子离子和小离子表示为在作为溶剂的介电连续体内具有不同大小的均匀带电硬球。该理论通过加权密度方法近似了硬球的贡献，而围绕均匀流体的功能扩展则用于离子部分。该理论定量地复制了各种系统参数的仿真数据。