Interfacial Hydration Dynamics in Cationic Micelles Using 2D-IR and NMR.

Using the thiocyanate anion as a vibrational probe chromophore in conjunction with infrared and NMR spectroscopy, we find that SCN strongly associates with the cationic head group of dodecyltrimethylammonium bromide (DTAB) micelles, both in normal-phase and reverse micelles. In competition with chloride and iodide ions, we find no evidence for displacement of thiocyanate, in accord with the chaotropicity of the Hofmeister ordering, while lending support to a direct interaction picture of its origin. Ultrafast 2D-IR spectroscopy of the SCN probe in a range of DTAB micelle sizes (w = 4 to w = 12) shows little if any size dependence on the time scale for spectral diffusion, which is found to be ∼3.5 times slower than in bulk water (both DO and HO). Normal-phase micelles studied with 2D-IR exhibit essentially the same spectral dynamics as do reverse micelles, indicating a lack of sensitivity to interfacial curvature. Combined with H NMR chemical shift perturbations, we conclude that the SCN ions tightly associate with the head groups and are partially buried. The 3-4-fold slowdown in spectral diffusion is consistent with the excluded volume model for interfacial perturbation to hydrogen bond reorientation dynamics. On the basis of these observations and comparisons to previous studies of zwitterionic interfaces probed with phosphate transitions, we conclude that the SCN spectral dynamics in both reverse- and normal-phase micelles is largely dominated by hydration contributions, and offers a promising probe of interfacial hydration at cationic interfaces. Addition of competitive anions alters neither the IR spectra nor the ultrafast dynamics, indicating that SCN is robustly associated with the head groups.