Supramolecular Packing Drives Morphological Transition of Charged Surfactant Micelles.

The shape and size of self-assembled structures upon local organization of their molecular building blocks are hard to predict in the presence of long-range interactions. Combining small-angle X-ray/neutron scattering data, theoretical modelling, and com- puter simulations, we investigate sodium dodecyl sulfate (SDS) in a broad range of concentrations and ionic strengths. Computer simulations indicate that micellar shape changes are associated with different binding of the counterions. Employing a toy model based on point charges on a surface, we demonstrate that the observed morphological changes are caused by symmetry breaking of the irreducible building blocks, with the formation of transient surfactant dimers mediated by the counterions that promote the stabilization of cylindrical instead of spherical micelles. The present model is of general applicability and can be extended to all systems controlled by the presence of mobile charges.