Rotational reorientation dynamics of aerosol-OT reverse micelles formed in nearcritical propane

The rotational reorientation kinetics of two fluorescent solutes (rhodamine 6G, R6G, and rhodamine 101, R101) have been determined in sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol-OT, AOT) reverse micelles formed in liquid and nearcritical propane. We show that the amount of water loading ([water]/[AOT], R), continuous phase density, and temperature all influence the solute rotational dynamics. In all cases, the decay of anisotropy data (i.e., frequency-dependent differential polarized phase angle and polarized modulation ratio) are well-described by a bi-exponential decay law. We find that the faster rotational correlation times are similar to but slightly less than the values predicted for an individual AOT reverse micelle rotating in propane. The recovered rotational correlation times range from 200 to 500 ps depending on experimental conditions. This faster rotational process is explained in terms of lateral diffusion of the fluorophore along the water/headgroup interfacial region within the reverse micelle. The recovered values for the slower rotational correlation times range from 7 to 18 ns. These larger rotational reorientation times are assigned to varying micelle-micelle (i.e., tail-tail) interactions in the low-density, highly compressible fluid region. We also quantify the contribution of the reverse micellar "aggregate" to the total decay of anisotropy.