Simulation of surfactant adsorption at liquid-liquid interface: What we may expect from soft-core models?

BF Faria and AM Vishnyakov, JOURNAL OF CHEMICAL PHYSICS, 157, 094706 (2022).

DOI: 10.1063/5.0087363

The present work attempts to systematically explore the surfactant sorption at liquid-liquid interfaces with coarse-grained models targeting thermodynamic properties of reference liquid solutions. We employ dissipative particle dynamics with soft-core forcefield tested against experimental data on micellization of surfactants in water, and the previous results are reproduced in this work. We consider three different nonionic surfactants: hexaethylene glycol monododecyl ether (C12E6), 2-4-(2,4,4-trimethylpentan-2-yl)phenoxyethanol) known as Triton X-100 (TX-100), and two alkyl glucoside surfactants (C(n)G(1)) with n-alkane tail fragments and a saccharide hydrophilic head at decane-water and toluene-water interfaces. For TX-100, we composed a model based on the literature forcefield and found good agreement with the experimental critical micelle concentrations (CMCs). The head-head interactions are of different origins for different surfactant groups: entropic repulsion between ethylene oxide chains of C12E6 and TX-100, and more chemically specific and complex interactions between the maltose heads of alkyl glucosides. We interpret our results with the Redlich-Peterson equation of monolayer adsorption in order to relate the adsorption to the bulk concentration of the surfactant and the interfacial tension. The densities of the adsorbed monolayer at CMC mostly agree with the experimental data, and a reasonable agreement was obtained for the interfacial tension at CMC. At the same time, we found significant discrepancies between the simulated and experimental adsorption isotherms. We explain them by the oversimplified forcefield: when the parameters are fitted to the free energies of bulk solutions, they may not correctly reproduce the interfacial free energies. Published under an exclusive license by AIP Publishing.

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