Phase transitions of fluorotelomer alcohols at the water|alkane interface studied molecular dynamics simulation

Fluorosurfactants are long-lasting environmental pollutants that accumulate at interfaces ranging from aerosol droplet surfaces to cell membranes. Modeling of adsorption-based removal technologies for fluorosurfactants requires accurate simulation methods which can predict their adsorption isotherm and monolayer structure. Fluorotelomer alcohols with one or two methylene groups adjacent to the alcohol (7 : 1 FTOH and 6 : 2 FTOH, respectively) are investigated using the OPLS-AA force field at the water|hexane interface, varying the interfacial area per surfactant. The acquired interfacial pressure isotherms and monolayer phase behavior are compared with previous experimental results. The results are consistent with the experimental data inasmuch as, at realistic adsorption densities, only 7 : 1 FTOH shows a phase transition between liquid-expanded (LE) and 2D crystalline phases. Structures of the LE and crystalline phases are in good agreement with the sticky disc and Langmuir defective crystal models, respectively, used previously to interpret experimental data. Interfacial pressure of the LE phase agrees well with experiment, and sticky disc interaction parameters indicate no 2D LE-gas transition is present for either molecule. Conformation analysis reveals 7 : 1 FTOH favors conformers where the OH dipole is perpendicular to the molecular backbone, such that the crystalline phase is stabilized when these dipoles align. Modeling of adsorption-based removal technologies for fluorosurfactants requires accurate simulation methods which can predict their adsorption isotherm and monolayer structure.