Fluorinated Propionic Acids Unmasked: Puzzling Fragmentation Phenomena of the Deprotonated Species

Environmental contamination by per- and polyfluorinated substances (PFAS) is an emerging concern for the public. In this study, short-chain PFAS such as deprotonated per- and polyfluorinated propionic acids are investigated using a combination of infrared multiple-photon dissociation (IRMPD) spectroscopy, collision-induced dissociation (CID), and density functional theory calculations. IRMPD and CID proceed via multiple competing pathways: (1) production of fluoroformate (FCO₂^-) and the associated ethylene derivative, (2) production of HF and the associated carbanion, or (3) loss of CO₂ and the associated carbanion. Fluorinated propionic acids with at least one fluorine atom bound to the terminal carbon yield FCO₂^-, whereas loss of HF is observed in polyfluorinated species with at least one fluorine atom bound to the α-carbon. To explore the reaction pathways of the various fluorinated propionic acids, the nudged elastic band method is employed. The relative energy of the four-membered ring transition state leading to FCO₂^- dictates which product channel is observed in dissociation.