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We present a short-range correction to the Coulomb potential to investigate the aggregation of amphiphilic molecules in aqueous solutions. The proposed modification allows to quantitatively reproduce the distribution of counterions above the critical micelle concentration (CMC) or, equivalently, the degree of ionization, α, of the micellar clusters. In particular, our theoretical framework has been applied to unveil the behavior of the cationic surfactant C24H49N2O2 (+) CH3SO4 (-), which offers a wide range of applications in the thriving and growing personal care market. A reliable and unambiguous estimation of α is essential to correctly understand many crucial features of the micellar solutions, such as their viscoelastic behavior and transport properties, in order to provide sound formulations for the above mentioned personal care solutions. We have validated our theory by performing extensive lattice Monte Carlo simulations, which show an excellent agreement with experimental observations. More specifically, our coarse-grained model is able to reproduce and predict the complex morphology of the micelles observed at equilibrium. Additionally, our simulation results disclose the existence of a transition from a monodisperse to a bidisperse size distribution of aggregates, unveiling the intriguing existence of a second CMC.

Effective short-range Coulomb correction to model the aggregation behavior of ionic surfactants