This work discusses a jellium scheme, built within the framework of the multicomponent Ornstein–Zernike (OZ) equation, which is capable of describing the collective structure of suspensions of highly charged colloids with added salt, even in the presence of finite-size multivalent microions. This approach uses a suitable approximation to decouple the microion–microion correlations from the macroion–microion profiles, which in combination with the methodology from the dressed ion theory (DIT) gives a full account of the electrostatic effective potential among the colloids. The main advantages of the present contribution reside in its ability to manage the short-range potentials and non-linear correlations among the microions, as well as its realistic characterization of the ionic clouds surrounding each macroion. The structure factors predicted by this jellium scheme are contrasted with previously reported experimental results for microgel suspensions with monovalent salts (2019 Phys. Rev. E 100 032602), thus validating its high accuracy in these situations. The present theoretical analysis is then extended to microgel suspensions with multivalent salts, which reveals the prominent influence of the counterion valence on the makeup of the effective potentials. Although the induced differences may be difficult to identify through the mesoscopic structure, our results suggest that the microgel collapsing transition may be used to enhance these distinct effects, thus giving a feasible experimental probe for these phenomena.

这项工作讨论了在多组分 Ornstein-Zernike (OZ) 方程框架内构建的果冻方案，该方案能够描述添加盐的高电荷胶体悬浮液的集体结构，即使存在有限尺寸的多价微离子. 该方法使用合适的近似值将微离子-微离子相关性与宏观离子-微离子分布图解耦，结合修饰离子理论 (DIT) 的方法，可以全面考虑胶体之间的静电有效电位。本贡献的主要优点在于它能够管理微离子之间的短程电位和非线性相关性，以及它对每个宏离子周围离子云的真实表征。物理。Rev. E 100 032602)，从而验证其在这些情况下的高精度。然后将当前的理论分析扩展到具有多价盐的微凝胶悬浮液，这揭示了反离子价对有效电位构成的显着影响。尽管通过细观结构可能难以识别诱导的差异，但我们的结果表明微凝胶塌陷转变可用于增强这些不同的效果，从而为这些现象提供了可行的实验探针。