Micelle Formation in Aqueous Solutions of Room Temperature Ionic Liquids: A Molecular Dynamics Study.

1-Alkyl-3-methylimidazolium cations in the presence of water are used as a test system to study by molecular dynamics the formation of micelles in aqueous mixtures of highly anisotropic room temperature ionic liquids (IL). Structural properties, i.e., radial distribution functions (RDF) and transport parameters, such as diffusion coefficients and conductivities, are computed as a function of the IL/water mole fraction. The concentration plots reveal a sharp change of the slope of both the cation self-diffusion coefficient and the first peak of the head-head RDF at approximately the same value of the concentration. This transition, considered as a measure of a critical micellar concentration, appears only for the most anisotropic systems, composed of longer alkyl chains. The formation of the micelles is confirmed from the analysis of the tail-tail and cation-water RDFs. As a general result, we found that the larger the anisotropy of the ionic liquid the lower the critical concentration and the larger the proportion of monomers forming part of the micelles. The molecular dynamics predictions are in line with the experimental evidence reported for these systems.