This study investigates critical structure-reactivity relationships within 34 representative per- and polyfluoroalkyl substances (PFASs) undergoing defluorination with UV-generated hydrated electrons. While C _nF_{2 n+1}-COO^- with variable fluoroalkyl chain lengths ( n = 2 to 10) exhibited a similar rate and extent of parent compound decay and defluorination, the reactions of telomeric C _nF_{2 n+1}-CH₂CH₂-COO^- and C _nF_{2 n+1}-SO₃^- showed an apparent dependence on the length of the fluoroalkyl chain. Cross comparison of experimental results, including different rates of decay and defluorination of specific PFAS categories, the incomplete defluorination from most PFAS structures, and the surprising 100% defluorination from CF₃COO^-, leads to the elucidation of new mechanistic insights into PFAS degradation. Theoretical calculations on the C-F bond dissociation energies (BDEs) of all PFAS structures reveal strong relationships among (i) the rate and extent of decay and defluorination, (ii) head functional groups, (iii) fluoroalkyl chain length, and (iv) the position and number of C-F bonds with low BDEs. These relationships are further supported by the spontaneous cleavage of specific bonds during calculated geometry optimization of PFAS structures bearing one extra electron, and by the product analyses with high-resolution mass spectrometry. Multiple reaction pathways, including H/F exchange, dissociation of terminal functional groups, and decarboxylation-triggered HF elimination and hydrolysis, result in the formation of variable defluorination products. The selectivity and ease of C-F bond cleavage highly depends on molecular structures. These findings provide critical information for developing PFAS treatment processes and technologies to destruct a wide scope of PFAS pollutants and for designing fluorochemical formulations to avoid releasing recalcitrant PFASs into the environment.

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