Microscopic structure and dynamics of interfacial water at fluorinated vs nonfluorinated surfaces—Insights from <i>ab-initio</i> simulations and IR spectroscopy

Abstract

Per- and polyfluoroalkyl substances are a class of synthetic chemical compounds widely used as coatings to lower surface energies. However, the microscopic mechanisms of their weak interaction with water and organic compounds remain poorly understood. Here, we perform large-scale density-functional-theory molecular dynamics simulations to investigate water at self-assembled monolayers (SAMs) of fluorinated and non-fluorinated hydrocarbons. We analyze the interfacial water structure and compare it to the prototypical hydrophobic air–water interface. The interfacial water structure at both SAMs closely resembles that at the air–water interface, featuring a distinct depletion layer and a two-dimensional hydrogen-bond network parallel to the surface. Computed anisotropic infrared spectra reproduce key experimental signatures observed in surface-enhanced infrared absorption spectroscopy, including the presence of free OH vibrations directly probing the local surface–water interactions. Notably, while the free OH stretch at the hydrocarbon SAM–water interface exhibits a red shift relative to the air–water interface, indicative of weak binding, the fluorinated SAM–water interface displays a weakly blue-shifted free OH mode. This frequency behavior defies common interpretations based on the vibrational Stark effect. Furthermore, we show that the reorientation dynamics of water molecules are significantly slower near the fluorinated surface, an effect rather expected at hydrophilic surfaces, which we link with spectral line shapes. Our results indicate that fluorinated SAMs, despite being macroscopically more hydrophobic than their unfluorinated counterparts, exhibit characteristics whose spectroscopic interpretation does not align with only hydrophobic or hydrophilic behavior.