Hydration layer of a cationic micelle, C₁₀TAB: structure, rigidity, slow reorientation, hydrogen bond lifetime, and solvation dynamics

We report a theoretical study of the structure and dynamics of the water layer (the hydration layer) present at the surface of the cationic micelle decyltrimethylammonium bromide (DeTAB) by using atomistic molecular dynamics simulations. The simulated micelle consisted of 47 surfactant molecules (and an equal number of bromide ions), in good agreement with the pioneering light scattering experiments by Debye which found an aggregation number of 50. In this micelle, three partially positively charged methyl groups of each surfactant headgroup face the surrounding water. The nature of the cationic micellar surface is found to play an important role in determining the arrangement of water which is quite different from that in the bulk or on the surface of an anionic micelle, like cesium perfluorooctanoate. Water molecules present in the hydration layer are found to be preferentially distributed in the region between the three partially charged methyl headgroups. It is found that both the translational and rotational motions of water exhibit appreciably slower dynamics in the layer than those in the bulk. The solvation time correlation function (TCF) of bromide ions exhibits a long time component which is found to originate primarily from the interaction of the probe with the micellar headgroups. Thus, the decay of the solvation TCF is controlled largely by the residence time of the probe in the surface. The residence time distribution of the water molecules also exhibits a slow time component. We also calculate the collective number density fluctuation in the layer and find a prominent slow component compared to the similar quantity in the bulk. This slow component demonstrates that water structure in the hydration layer is more rigid than that in the bulk. These results demonstrate that the slow dynamics of hydration layer water is generic to macromolecular surfaces of either polarity