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On the origin of oscillatory interactions between surfaces mediated by polyelectrolyte solution

Jiang, Jian and Ginzburg, Valeriy V. and Wang, Zhen-Gang (2019) On the origin of oscillatory interactions between surfaces mediated by polyelectrolyte solution. Journal of Chemical Physics, 151 (21). Art. No. 214901. ISSN 0021-9606. doi:10.1063/1.5123172. https://resolver.caltech.edu/CaltechAUTHORS:20191202-105354237

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Abstract

We use a numerical implementation of polymer classical density functional theory with an incompressibility condition to study the system consisting of nonadsorbing polyelectrolytes confined by two planar surfaces and quantify the effective interaction between the two planar surfaces as a function of the polyelectrolyte and salt concentrations. Our results indicate that for the uncharged surfaces (and weakly charged surfaces), the effective interaction primarily consists of a short-range attraction due to the depletion followed by repulsion due to the electric double layer overlapping and electrostatic correlations. For salt-free and low salt concentration systems, the magnitude of the repulsion barrier is determined by the overlap between the electric double layers, while at relatively high salt concentrations, the magnitude of the repulsion barrier is determined by the electrostatic correlations. Due to the competition between the electric double layer and the electrostatic correlations, the magnitude of the repulsion barrier varies nonmonotonically. In contrast, a mean-field Poisson-Boltzmann treatment of the electrostatics predicts a monotonically decreasing repulsion barrier with increasing salt concentration. At moderate salt concentrations, our theory predicts oscillatory interaction profiles. A comparison with the mean-field Poisson-Boltzmann treatment of electrostatics suggests that the oscillations are due primarily to electrostatic correlations.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/1.5123172DOIArticle
ORCID:
AuthorORCID
Ginzburg, Valeriy V.0000-0002-2775-5492
Wang, Zhen-Gang0000-0002-3361-6114
Additional Information:© 2019 Published under license by AIP Publishing. Submitted: 5 August 2019; Accepted: 13 November 2019; Published Online: 2 December 2019. The Dow Chemical Company is acknowledged for funding and for permission to publish the results.
Funders:
Funding AgencyGrant Number
Dow Chemical CompanyUNSPECIFIED
Issue or Number:21
DOI:10.1063/1.5123172
Record Number:CaltechAUTHORS:20191202-105354237
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20191202-105354237
Official Citation:On the origin of oscillatory interactions between surfaces mediated by polyelectrolyte solution. Jian Jiang, Valeriy V. Ginzburg, and Zhen-Gang Wang. The Journal of Chemical Physics 151:21. https://doi.org/10.1063/1.5123172
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:100136
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:02 Dec 2019 20:31
Last Modified:16 Nov 2021 17:51

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