Prediction of the Critical Micelle Concentration of Nonionic Surfactants by Dissipative Particle Dynamics Simulations.

Micellization of surfactant solutions is a ubiquitous phenomenon in natural systems and technological processes, and its theoretical description represents one of the cornerstone problems in the physical chemistry of colloidal systems. However, successful attempts of quantitative modeling confirmed by experimental data remains limited. We show, for the first time, that the dissipative particle dynamics with rigorously defined soft repulsion interaction and rigidity parameters is capable of predicting micellar self-assembly of nonionic surfactants. This is achieved due to a novel approach suggested for defining the interaction parameters by fitting to the infinite dilution activity coefficients of binary solutions formed by reference compounds that represent coarse-grained fragments of surfactant molecules. Using this new parametrization scheme, we obtained quantitative agreement with the experimental critical micelle concentration and aggregation number for several typical surfactants of different chemical structures. The proposed approach can be extended to various colloidal and polymeric systems beyond nonionic surfactant solutions.