Micelle Formation in Alkyl Sulfate Surfactants Using Dissipative Particle Dynamics.

We use dissipative particle dynamics (DPD) to study micelle formation in alkyl sulfate surfactants, with alkyl chain lengths ranging from 6 to 12 carbon atoms. We extend our recent DPD force field [ J. Chem. Phys. 2017 , 147 , 094503 ] to include a charged sulfate chemical group and aqueous sodium ions. With this model, we achieve good agreement with the experimentally reported critical micelle concentrations (CMCs) and can match the trend in mean aggregation numbers versus alkyl chain length. We determine the CMC by fitting a charged pseudophase model to the dependence of the free surfactant on the total surfactant concentration above the CMC and compare it with a direct operational definition of the CMC as the point at which half of the surfactant is classed as micellar and half as monomers and submicellar aggregates. We find that the latter provides the best agreement with experimental results. Finally, with the same model, we are able to observe the sphere-to-rod morphological transition for sodium dodecyl sulfate (SDS) micelles and determine that it corresponds to SDS concentrations in the region of 300-500 mM.