Characterization of dynamics and mechanism in the self-assembly of AOT reverse micelles

Reverse micelles (RMs) are recognized as a paradigm of molecular self-assembly and used in a variety of applications, such as chemical synthesis and molecular structure refinement. Nevertheless, many fundamental properties including their equilibrium size distribution, internal structure, and mechanism of self-assembly remain poorly understood. To provide an enhanced microscopic understanding of the assembly process and resulting structural distribution, we perform multiple nonequilibrium molecular dynamics simulations of dioctyl sulfosuccinate sodium salt (AOT) RM assembly, quantifying RM size, water core structure, and dynamics. Rapid assembly of smaller RM from a random mixture is observed to establish a constant AOT water loading within a nanosecond consistent with a diffusion-adsorption mechanism validated through the Monte-Carlo simulation of a model system. The structure of RM water cores and RM molecular volume during RM assembly is characterized during the AOT assembly process. A moment-closure equation is developed from a novel master equation model to elucidate the elementary events underlying the AOT self-assembly process. The resulting kinetic model is used to explore the role of monomer addition and dissociation, RM association and dissociation, and RM collision-induced exchange, all dependent on average RM size, which provides fundamental insight regarding the mechanisms and time scales for AOT RM self-assembly. The nascent dynamics that rapidly establish water loading, intermediate time scales of RM fusion, and longer time scale dynamics of inter-RM exchange essential in establishing the equilibrium condition are quantified through these kinetic models. Overall, this work provides insight into AOT RM self-assembly and provides a general theoretical framework for the analysis of the molecular self-assembly dynamics and mechanism.