Electrostatic Screening and Charge Correlation Effects in Micellization of Ionic Surfactants

Handle URI:
http://hdl.handle.net/10754/598152
Title:
Electrostatic Screening and Charge Correlation Effects in Micellization of Ionic Surfactants
Authors:
Jusufi, Arben; Hynninen, Antti-Pekka; Haataja, Mikko; Panagiotopoulos, Athanassios Z.
Abstract:
We have used atomistic simulations to study the role of electrostatic screening and charge correlation effects in self-assembly processes of ionic surfactants into micelles. Specifically, we employed grand canonical Monte Carlo simulations to investigate the critical micelle concentration (cmc), aggregation number, and micellar shape in the presence of explicit sodium chloride (NaCl). The two systems investigated are cationic dodecyltrimethylammonium chloride (DTAC) and anionic sodium dodecyl sulfate (SDS) surfactants. Our explicit-salt results, obtained from a previously developed potential model with no further adjustment of its parameters, are in good agreement with experimental data for structural and thermodynamic micellar properties. We illustrate the importance of ion correlation effects by comparing these results with a Yukawa-type surfactant model that incorporates electrostatic screening implicitly. While the effect of salt on the cmc is well-reproduced even with the implicit Yukawa model, the aggregate size predictions deviate significantly from experimental observations at low salt concentrations. We attribute this discrepancy to the neglect of ion correlations in the implicit-salt model. At higher salt concentrations, we find reasonable agreement of the Yukawa model with experimental data. The crossover from low to high salt concentrations is reached when the electrostatic screening length becomes comparable to the headgroup size. © 2009 American Chemical Society.
Citation:
Jusufi A, Hynninen A-P, Haataja M, Panagiotopoulos AZ (2009) Electrostatic Screening and Charge Correlation Effects in Micellization of Ionic Surfactants. J Phys Chem B 113: 6314–6320. Available: http://dx.doi.org/10.1021/jp901032g.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry B
KAUST Grant Number:
KUS-CI-018-02
Issue Date:
7-May-2009
DOI:
10.1021/jp901032g
PubMed ID:
19361177
Type:
Article
ISSN:
1520-6106; 1520-5207
Sponsors:
This publication is based on work supported by the Princeton Center for Complex Materials (Grant NSF DMR 0213706), the Department of Energy (Grant DE-FG02-01ER15121), and by Award No. KUS-CI-018-02, made by King Abdullah University of Science and Technology (KAUST). A.J. gratefully acknowledges financial support from the Deutsche Forschungsgemeinschaft.
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Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorJusufi, Arbenen
dc.contributor.authorHynninen, Antti-Pekkaen
dc.contributor.authorHaataja, Mikkoen
dc.contributor.authorPanagiotopoulos, Athanassios Z.en
dc.date.accessioned2016-02-25T13:13:41Zen
dc.date.available2016-02-25T13:13:41Zen
dc.date.issued2009-05-07en
dc.identifier.citationJusufi A, Hynninen A-P, Haataja M, Panagiotopoulos AZ (2009) Electrostatic Screening and Charge Correlation Effects in Micellization of Ionic Surfactants. J Phys Chem B 113: 6314–6320. Available: http://dx.doi.org/10.1021/jp901032g.en
dc.identifier.issn1520-6106en
dc.identifier.issn1520-5207en
dc.identifier.pmid19361177en
dc.identifier.doi10.1021/jp901032gen
dc.identifier.urihttp://hdl.handle.net/10754/598152en
dc.description.abstractWe have used atomistic simulations to study the role of electrostatic screening and charge correlation effects in self-assembly processes of ionic surfactants into micelles. Specifically, we employed grand canonical Monte Carlo simulations to investigate the critical micelle concentration (cmc), aggregation number, and micellar shape in the presence of explicit sodium chloride (NaCl). The two systems investigated are cationic dodecyltrimethylammonium chloride (DTAC) and anionic sodium dodecyl sulfate (SDS) surfactants. Our explicit-salt results, obtained from a previously developed potential model with no further adjustment of its parameters, are in good agreement with experimental data for structural and thermodynamic micellar properties. We illustrate the importance of ion correlation effects by comparing these results with a Yukawa-type surfactant model that incorporates electrostatic screening implicitly. While the effect of salt on the cmc is well-reproduced even with the implicit Yukawa model, the aggregate size predictions deviate significantly from experimental observations at low salt concentrations. We attribute this discrepancy to the neglect of ion correlations in the implicit-salt model. At higher salt concentrations, we find reasonable agreement of the Yukawa model with experimental data. The crossover from low to high salt concentrations is reached when the electrostatic screening length becomes comparable to the headgroup size. © 2009 American Chemical Society.en
dc.description.sponsorshipThis publication is based on work supported by the Princeton Center for Complex Materials (Grant NSF DMR 0213706), the Department of Energy (Grant DE-FG02-01ER15121), and by Award No. KUS-CI-018-02, made by King Abdullah University of Science and Technology (KAUST). A.J. gratefully acknowledges financial support from the Deutsche Forschungsgemeinschaft.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleElectrostatic Screening and Charge Correlation Effects in Micellization of Ionic Surfactantsen
dc.typeArticleen
dc.identifier.journalThe Journal of Physical Chemistry Ben
dc.contributor.institutionPrinceton University, Princeton, United Statesen
kaust.grant.numberKUS-CI-018-02en

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