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Title: Explicit- and Implicit-Solvent Simulations of Micellization in Surfactant Solutions

Abstract

Here, we focus on simulation methodologies to obtain the critical micelle concentration (cmc) and equilibrium distribution of aggregate sizes in dilute surfactant solutions. Even though it is now relatively easy to obtain micellar aggregates in simulations starting from a fully dispersed state, several major challenges remain. In particular, the characteristic times of micelle reorganization and transfer of monomers from micelles to free solution for most systems of practical interest exceed currently accessible molecular dynamics time scales for atomistic surfactant models in explicit solvent. In addition, it is impractical to simulate highly dilute systems near the cmc. We have demonstrated a strong dependence of the free surfactant concentration (frequently, but incorrectly, taken to represent the cmc in simulations) on the overall concentration for ionic surfactants. We have presented a theoretical framework for making the necessary extrapolations to the cmc. We find that currently available atomistic force fields systematically underpredict experimental cmc’s, pointing to the need for the development of improved models. For strongly micellizing systems that exhibit strong hysteresis, implicit-solvent grand canonical Monte Carlo simulations represent an appealing alternative to atomistic or coarse-grained, explicit-solvent simulations. We summarize an approach that can be used to obtain quantitative, transferrable effective interactions and illustratemore » how this grand canonical approach can be used to interpret experimental scattering results.« less

Authors:
 [1];  [2]
+ Show Author Affiliations
  1. City Univ. (CUNY), NY (United States). College of Staten Island and Graduate Center and Dept. of Chemistry
  2. Princeton Univ., NJ (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1159191
Alternate Identifier(s):
OSTI ID: 1459162
Grant/Contract Number:  
SC0002128; DMR-0819860
Resource Type:
Published Article
Journal Name:
Langmuir
Additional Journal Information:
Journal Name: Langmuir Journal Volume: 31 Journal Issue: 11; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jusufi, Arben, and Panagiotopoulos, Athanassios Z. Explicit- and Implicit-Solvent Simulations of Micellization in Surfactant Solutions. United States: N. p., 2014. Web. doi:10.1021/la502227v.
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Jusufi, Arben, & Panagiotopoulos, Athanassios Z. Explicit- and Implicit-Solvent Simulations of Micellization in Surfactant Solutions. United States. https://doi.org/10.1021/la502227v
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Jusufi, Arben, and Panagiotopoulos, Athanassios Z. Tue . "Explicit- and Implicit-Solvent Simulations of Micellization in Surfactant Solutions". United States. https://doi.org/10.1021/la502227v.
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@article{osti_1159191,
title = {Explicit- and Implicit-Solvent Simulations of Micellization in Surfactant Solutions},
author = {Jusufi, Arben and Panagiotopoulos, Athanassios Z.},
abstractNote = {Here, we focus on simulation methodologies to obtain the critical micelle concentration (cmc) and equilibrium distribution of aggregate sizes in dilute surfactant solutions. Even though it is now relatively easy to obtain micellar aggregates in simulations starting from a fully dispersed state, several major challenges remain. In particular, the characteristic times of micelle reorganization and transfer of monomers from micelles to free solution for most systems of practical interest exceed currently accessible molecular dynamics time scales for atomistic surfactant models in explicit solvent. In addition, it is impractical to simulate highly dilute systems near the cmc. We have demonstrated a strong dependence of the free surfactant concentration (frequently, but incorrectly, taken to represent the cmc in simulations) on the overall concentration for ionic surfactants. We have presented a theoretical framework for making the necessary extrapolations to the cmc. We find that currently available atomistic force fields systematically underpredict experimental cmc’s, pointing to the need for the development of improved models. For strongly micellizing systems that exhibit strong hysteresis, implicit-solvent grand canonical Monte Carlo simulations represent an appealing alternative to atomistic or coarse-grained, explicit-solvent simulations. We summarize an approach that can be used to obtain quantitative, transferrable effective interactions and illustrate how this grand canonical approach can be used to interpret experimental scattering results.},
doi = {10.1021/la502227v},
journal = {Langmuir},
number = 11,
volume = 31,
place = {United States},
year = {Tue Sep 16 00:00:00 EDT 2014},
month = {Tue Sep 16 00:00:00 EDT 2014}
}
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https://doi.org/10.1021/la502227v
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