The role of helicity in PFAS resistance to degradation: DFT simulation of electron capture and defluorination

Defluorination of perfluorinated alkyl substances (PFASs) via the direct capture of excess electrons poses a promising path to environmental decontamination. Herein we show that ab initio model optimization methods can be adapted to simulate the changes to molecular geometry that result from electron capture. These reaction pathways demonstrate that the introduction of an additional electron causes a loss of the helical arrangement along linear carbon tail chains. Regaining helicity is sufficiently favourable to enable fluoride release in C7-C10 carboxylate or sulfonate PFAS chains; shorter chains are enthalpically hindered from degradation while the additional charge is stabilized on longer chains by the greater entropy their flexibility permits. These results suggest that reductive PFAS treatment processes could be made more effective under high pressure or confined conditions.