Hidden Beneath the Layers: Extending the Core/Shell Model of Reverse Micelles.

Reverse micelles (RMs) provide a unique and highly tunable model system to study water in confined environments. The complex properties of water within RMs arise from the disruption of extended hydrogen bond (H-bond) networks that mediate local and long-range dynamics in bulk aqueous systems. Modulating the water pool size influences its H-bond dynamics, with smaller RMs increasingly restricting the H-bond network rearrangements leading to slower dynamics; however, within small confined systems, the dynamics of the surfactants also influence the water dynamics. Using ultrafast two-dimensional infrared spectroscopy, we investigate the effects of RM size on the surfactant headgroup rotamer populations and picosecond interfacial H-bond dynamics of aerosol-OT surfactants. We find that the increased water penetration accelerates H-bond dynamics, with larger RMs showing faster dynamics. These results imply that the changes in the RM structure alter the physical structure of the RM interface and thus alter the solvation dynamics. The findings in this study can be used for developing models for structure-specific solvation dynamics that account for the surfactant packing and hydration at the interface.