Sphere versus cylinder: the effect of packing on the structure of nonionic C12E6 micelles

Two independent series of calculations are performed simulating spherical and cylindrical C12E6 micelles in a temperature range around the experimental sphere-to-rod transition temperature for surfactant concentrations less than 20% by weight. A comparative analysis of these systems helps to shed light on the microscopic details of the micelle sphere-to-rod transition. In agreement with theoretical models, we find that spherical and cylindrical micelles have a different oil core packing; the core radius of a cylindrical micelle is reduced by a factor of 0.87 with respect to the core radius of a spherical micelle. Despite this contraction, the specific volume of the alkyl tails is larger in a cylindrical micelle than in a spherical micelle. In both geometries, this specific volume follows the same linear increase with temperature. Density measurement experiments are also performed in order to evaluate the specific volume of the hydrophobic tail of surfactants of the C12Ej family with j ranging from 5 to 8. We observe a good agreement between experimental data and simulation results. Our simulations also show that the spatial distribution of the head groups in the interface is more effective in screening the oil core in the cylindrical aggregate than in the spherical aggregate, reducing by a factor of 2 the oil surface per monomer exposed to water. This screening accounts for a free-energy difference of Deltafs=fssph-fscyl approximately +2.5kBT per monomer and mirrors the essential role that the hydrophobic interactions have on the shape transition. We also find that the different interface packing correlates with different conformations and flexibility of the hydrophilic fragments E6, that appear as an entropic reservoir for the transition. Finally, comparing the degree of hydration of a spherical micelle at T=283 K with that of a cylindrical micelle at T=318 K, we observe an amount of dehydration in agreement with reported experimental data across the sphere-to-rod transition. However, for aggregates of fixed shape, we find a much smaller amount of dehydration with temperature, suggesting that the shape transition is not a consequence of the measured temperature dehydration but rather the opposite.