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Thermochemistry of per‐ and polyfluoroalkyl substances
Author(s) -
Melin Timothé R. L.,
Harell Preston,
Ali Betoul,
Loganathan Narasimhan,
Wilson Angela K.
Publication year - 2023
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.27023
Subject(s) - thermochemistry , chemistry , gas phase , ab initio , standard enthalpy of formation , density functional theory , atmosphere (unit) , computational chemistry , thermodynamics , molecule , phase (matter) , ab initio quantum chemistry methods , organic chemistry , physics
The determination of gas phase thermochemical properties of per‐ and polyfluoroalkyl substances (PFAS) is central to understanding the long‐range transport behavior of PFAS in the atmosphere. Prior gas‐phase studies have reported the properties of perfluorinated sulfonic acid (PFOS) and perfluorinated octanoic acid (PFOA). Here, this study reports the gas phase enthalpies of formation of short‐ and long‐chain PFAS and their precursor molecules determined using density functional theory (DFT) and ab initio approaches. Two density functionals, two ab initio methods and an empirical method were used to compute enthalpies of formation with the total atomization approach and an isogyric reaction. The performance of the computational methods employed in this work were validated against the experimental enthalpies of linear alkanoic acids and perfluoroalkanes. The gas‐phase determinations will be useful for future studies of PFAS in the atmosphere, and the methodological choices will be helpful in the study of other PFAS.