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

Jusufi, Arben; Panagiotopoulos, Athanassios Z.

doi:10.1021/la502227v

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

Journal Article · Tue Sep 16 00:00:00 EDT 2014 · Langmuir

DOI:https://doi.org/10.1021/la502227v· OSTI ID:1159191

Jusufi, Arben ^[1]; Panagiotopoulos, Athanassios Z. ^[2]

City Univ. (CUNY), NY (United States). College of Staten Island and Graduate Center and Dept. of Chemistry
Princeton Univ., NJ (United States). Dept. of Chemical and Biological Engineering

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.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0002128; DMR-0819860

OSTI ID:: 1159191

Alternate ID(s):: OSTI ID: 1459162

Journal Information:: Langmuir, Journal Name: Langmuir Vol. 31 Journal Issue: 11; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 27 works

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