Dynamics in the Interior of AOT Lamellae Investigated with Two-Dimensional Infrared Spectroscopy

The dynamics inside the organic regions of aerosol-OT (AOT)/water mixtures in the lamellar mesophase, bicontinuous cubic (BC) phase, and in an analogous molecule without the charged sulfonate headgroup are investigated by observing spectral diffusion, orientational relaxation and population relaxation using ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy and IR pump-probe experiments on the asymmetric CO stretch of a vibrational probe, tungsten hexacarbonyl (W(CO)(6)). The water layer thickness between the bilayer planes in the lamellar phase was varied. For comparison, the dynamics of W(CO)(6) in the normal liquid bis(2-ethylhexyl) succinate (EHS), which is analogous to AOT but has no charged sulfonate headgroup, were also studied. The 2D IR experiments measure spectral diffusion, which results from the structural evolution of the system. Spectral diffusion is quantified by the frequency-frequency correlation function (FFCF). In addition to a homogeneous component, the FFCFs are biexponential decays with fast and slow time components of similar to 12.5 and similar to 150 ps in the lamellar phase. Both components of the FFCF are independent of the number of water molecules per headgroup for the lamellae, but they slow somewhat in the BC phase. The dynamics in the ordered phases are in sharp contrast to the dynamics in EHS, which displays fast and slow components of the FFCF of 5 and 80 ps, respectively. As the hydration level of AOT increases, vibrational lifetime decreases, suggesting some change in the local environment of W(CO)(6) with water content.