DPD simulations of anionic surfactant micelles: a critical role for polarisable water models

Abstract

We investigate the effects of polarisable water models in dissipative particle dynamics (DPD) simulations, focussing on the influence these models have on the aggregation behaviour of sodium dodecyl sulfate solutions. Studies in the literature commonly report that DPD approaches underpredict the micellar aggregation number of ionic surfactants compared to experimental values. One of the proposed reasons for this discrepancy is that existing water models are insufficient to accurately model micellar solutions, as they fail to account for structural changes in water close to micellar surfaces. We show that polarisable DPD water models lead to more realistic counterion behaviour in micellar solutions, including the degree of counterion disassociation. These water models can also accurately reproduce changes in the dielectric constant of surfactant solutions as a function of concentration. We find evidence that polarisable water leads to the formation of more stable micelles at higher aggregation numbers. However, we also show that the choice of water model is not responsible for the underestimated aggregation numbers observed in DPD simulations. This finding addresses a key question in the literature surrounding the importance of water models in DPD simulations of ionic micellar solutions.