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浓电解质中可极化胶体的平均力势能与欠屏蔽效应

Potential of Mean Force and Underscreening of Polarizable Colloids in Concentrated Electrolytes.

作者信息

Krucker-Velasquez Emily, Bazant Martin Z, Alexander-Katz Alfredo, Swan James W

机构信息

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

出版信息

Nano Lett. 2025 Jul 2;25(26):10362-10368. doi: 10.1021/acs.nanolett.5c01541. Epub 2025 Jun 18.

DOI:10.1021/acs.nanolett.5c01541
PMID:40534272
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12226989/
Abstract

This study uses advanced numerical methods to estimate the mean force potential (PMF) between charged, polarizable colloidal particles in dense electrolytes. We observe that when the Debye screening length, λ, is below the hydrated ion size, the PMF shows discernible oscillations of purely electrostatic origin as opposed to chemical affinity, in addition to the expected exponential decay prescribed by Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Moreover, our findings suggest concentrated electrolytes are significantly less efficient at muting electrostatic interactions in electrostatically stabilized colloidal suspensions, potentially having significant implications for our understanding of colloidal stability and the forces that govern the behavior of concentrated charged soft matter systems beyond DLVO theory.

摘要

本研究采用先进的数值方法来估算浓电解质中带电、可极化胶体颗粒之间的平均力势(PMF)。我们观察到,当德拜屏蔽长度λ低于水合离子大小时,除了德亚金-朗道-韦弗-奥弗贝克(DLVO)理论规定的预期指数衰减外,PMF还表现出纯粹由静电起源而非化学亲和力引起的明显振荡。此外,我们的研究结果表明,在静电稳定的胶体悬浮液中,浓电解质在减弱静电相互作用方面的效率要低得多,这可能对我们理解胶体稳定性以及超出DLVO理论的支配浓带电软物质系统行为的力具有重大意义。