Molecular Thermodynamics for Micellar Branching in Solutions of Ionic Surfactants

We develop an analytical molecular-thermodynamic model for the aggregation free energy of branching portions of wormlike ionic micelles in 1:1 salt solution. The junction of three cylindrical aggregates is represented by a combination of pieces of the torus and bilayer. A geometry-dependent analytical solution is obtained for the linearized Poisson−Boltzmann equation. This analytical solution is applicable to saddle-like structures and reduces to the solutions known previously for planar, cylindrical, and spherical aggregates. For micellar junctions, our new analytical solution is in excellent agreement with numerical results over the range of parameters typical of ionic surfactant systems with branching micelles. Our model correctly predicts the sequence of stable aggregate morphologies, including a narrow bicontinuous zone, in dependence of hydrocarbon tail length, head size, and solution salinity. For predicting properties of a spatial network of wormlike micelles, our aggregation free energy is used in the Zilman−Safran theory. Our predictions are compared with experimental data for branching micelles of ionic surfactants.