Structural Insights into Self-Assembled Aerosol-OT Aggregates in Aqueous Media Using Atomistic Molecular Dynamics

In water, the surfactant dioctyl sulfosuccinate (Aerosol-OT or AOT) exhibits diverse aggregate structures, ranging from micelles to lamella. An atomic-level understanding, however, of the formation and structure of these aggregates is lacking. Herein, using atomistic molecular dynamics (MD) with microsecond-long simulations, self-assembly of AOT in water is studied for concentrations of 1, 7.2, and 20 wt % at 293 K and for 7.2 wt % at 353 K. Assembly proceeds through stepwise association and dissociation of single AOT molecules, and the fusion and fission of AOT clusters. At 293 K, AOT self-assembles into either (i) spherical micelles (1 wt %), (ii) biphasic systems consisting of rod-like and prolate spheroidal micelles (7.2 wt %), or (iii) bilayers (20 wt %). We hypothesize that the observed rod-like structure is a precursor to lamellar microdomains found experimentally in biphasic dispersions. Increasing temperature to 353 K at 7.2 wt % results in a system consisting of prolate micelles but no rod-like micelles. Simulated phase behavior agrees with previously published experimental observations. Individual aggregates formed during self-assembly are identified using graph theory. Structural metrics of these aggregates like the radius of gyration, shape anisotropy, and prolateness are presented. Trends in structural metrics quantitatively reflect how shapes and sizes of AOT aggregates vary with surfactant concentration and temperature. These simulations provide deeper insight into open questions in the scientific community and demonstrate a method to generate physics-based micelle structures that can be used to rationalize experimental observations.