A Coarse-Grained Model Describing the Critical Micelle Concentration of Perfluoroalkyl Surfactants in Ionic Aqueous Phase

In this study, dissipative particle dynamics (DPD) simulations were employed to determine the critical micelle concentration (CMC) of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in ionic aqueous solutions. This approach provides precise CMC data for PFAS surfactants in the presence of various ionic species, thereby addressing a gap in the current literature. Additionally, this study contributes to the development of open-source molecular force fields for charged perfluorinated compounds, which are currently limited. These models incorporate hydration free energy values obtained from density functional theory (DFT) and account for ionic interactions through a well-established linear relationship. Hydrophobic interactions between the surfactant tail and water were fine-tuned to match the CMC of chosen surfactants. Then, the DPD models successfully predicted CMC values for a diverse range of surfactants, including those based on hydrocarbons and PFAS, demonstrating the ability to represent realistic salinities encountered in natural waters. Experimental validation of the methodology was conducted using sodium <i>n</i>-nonyl sulfate (SNS) and sodium <i>n</i>-dodecyl sulfate (SDS) via interfacial tension measurements, confirming the accurate representation of the CMC changes with salinity. This study enhances our understanding of the behavior of PFAS surfactants in ionic aqueous solutions and provides a valuable tool for predicting CMC values in complex environmental systems.