Publication: Comparative theoretical investigation on the isomerization energies of long-chain perfluoroalkanes: A case study with perfluorooctanoic acid congeners

All || By Area || By Year

Title	Comparative theoretical investigation on the isomerization energies of long-chain perfluoroalkanes: A case study with perfluorooctanoic acid congeners
Authors/Editors*	S Rayne, K Forest
Where published*	Nature Precedings
How published*	Other
Year*	2011
Volume
Number
Pages
Publisher	Nature Publishing Group
Keywords	thermodynamic stability; perfluoroalkanes; perfluorooctanoic acid (PFOA); theoretical study
Link	http://dx.doi.org/10.1038/npre.2011.5528.1
Abstract	The gas and solution phase relative thermodynamic stabilities of the 39 linear and branched perfluorooctanoic acid (PFOA) congeners in both their acid and anionic forms were calculated at various levels of density functional (B3LYP, wB97XD, and M062X functionals with the 6-311++G(d,p) basis set) and second order Moller-Plesset perturbation (MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p)) theory using the SMD implicit solvation model. The B3LYP functional does not accurately model the expected trends in thermodynamic stability of PFOA isomers with linear versus branched perfluoroalkyl chains. Calculations obtained with the M062X and MP2 model chemistries suggest these theoretical methods may be more appropriate for relative thermodynamic stability studies on various perfluoroalkyl compounds.