Molecular Interactions of Perfluorinated and Branched Fluorine-Free Surfactants at Interfaces: Insights from a New Reliable Force Field.

Per- and polyfluoroalkyl substances (PFAS) constitute a class of synthetic compounds with exceptional interfacial properties. Their widespread use in many industrial applications and consumer products, combined with their remarkable chemical and thermal stability, has led to their ubiquitous presence in environmental matrices, including surface water and groundwater. To replace PFAS with fluorine-free surfactants, it is necessary first to develop a deep molecular-level understanding of the mechanisms responsible for the exceptional properties of PFAS. For instance, it has been shown that fluorine-free surfactants with highly branched or methylated chains can achieve low surface tensions at air-water interfaces and can provide highly hydrophobic surface coatings. Although molecular simulations combined with experiments are promising for uncovering these mechanisms, the reliability of simulation results depends strongly on the accuracy of the force fields implemented. At the moment, atomistic force fields are not available to describe PFAS in a variety of environments. Ab initio methods could help fill this knowledge gap, but they are computationally demanding. As an alternative, ab initio calculations could be used to develop accurate force fields for atomistic simulations. In this work, a new algorithm is proposed, which, built from accurate ab initio calculations, yields force fields for perfluorinated sulfonic and perfluoroalkyl acids. The accuracy of the new force field was benchmarked against solvation free energy and interfacial tension data. The new force fields were then used to probe the interfacial behavior of the PFAS surfactants. The interfacial properties observed in our simulations were compared with those manifested by two branched fluorine-free surfactants. The good agreement achieved with experiments and ab initio calculations suggests that the proposed protocol could be implemented to study other perfluorinated substances and help in the design of fluorine-free surfactants for targeted applications.