Effective interactions, structure, and pressure in charge-stabilized colloidal suspensions: Critical assessment of charge renormalization methods

重整化 电荷(物理) 胶体 统计物理学 有效核电荷 化学物理 材料科学 凝聚态物理 物理 化学 量子力学 离子 物理化学
作者
Mariano Brito,Gerhard Nägele,Alan R. Denton
出处
期刊:Journal of Chemical Physics [American Institute of Physics]
卷期号:159 (20)
标识
DOI:10.1063/5.0180914
摘要

Charge-stabilized colloidal suspensions display a rich variety of microstructural and thermodynamic properties, which are determined by electro-steric interactions between all ionic species. The large size asymmetry between molecular-scale microions and colloidal macroions allows the microion degrees of freedom to be integrated out, leading to an effective one-component model of microion-dressed colloidal quasi-particles. For highly charged colloids with strong macroion-microion correlations, nonlinear effects can be incorporated into effective interactions by means of charge renormalization methods. Here, we compare and partially extend several practical mean-field methods of calculating renormalized colloidal interaction parameters, including effective charges and screening constants, as functions of concentration and ionic strength. Within the one-component description, we compute structural and thermodynamic properties from the effective interactions and assess the accuracy of the different methods by comparing predictions with elaborate primitive-model simulations [P. Linse, J. Chem. Phys. 113, 4359 (2000)]. We also compare various prescriptions for the osmotic pressure of suspensions in Donnan equilibrium with a salt ion reservoir and analyze instances where the macroion effective charge becomes larger than the bare one. The methods assessed include single-center cell, jellium, and multi-center mean-field theories. The strengths and weaknesses of the various methods are critically assessed, with the aim of guiding optimal and accurate implementations.
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