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Thermodynamic stability of neutral and anionic PFOAs

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Abstract

The thermodynamic stability of the PFOA family of 39 structural isomers was studied using the M06-2X, LC-ωPBE, B97D and B3LYP functionals and with the PM6 method. The PM6 results closely resemble the M06-2X results for neutral PFOAs, but diverge strongly in regard to anions. The four functionals applied behave similarly from a qualitative point of view, but quantitatively speaking, the LC-ωPBE and B97D results are somewhere between the M06-2X and B3LYP stability results. M06-2X ranks highly substituted isomers as more stable than did B3LYP and ranks less branched isomers quite low in relative stability compared to B3LYP. Various similarities with a former PFOSs study applying the M06-2X and B3LYP functionals have been identified. The degree of branching within structural isomers cannot always be precisely determined, and it is not the only aspect that determines thermodynamic stability, as the pattern of substitution also seems to play a significant role.

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Acknowledgments

The authors gratefully acknowledge the Natural Sciences and Engineering Research Council of Canada (NSERC) for financial support and would like to thank Information Technology Services at Thompson Rivers University.

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Authors and Affiliations

  1. Department of Chemistry, University of Victoria, Victoria, BC, V8P 5C2, Canada

    Abdel Hidalgo & Nelaine Mora-Diez

  2. Department of Chemistry, Thompson Rivers University, Kamloops, BC, V2C 0C8, Canada

    Thomas Giroday & Nelaine Mora-Diez

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  1. Abdel Hidalgo
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Correspondence to Nelaine Mora-Diez.

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Hidalgo, A., Giroday, T. & Mora-Diez, N. Thermodynamic stability of neutral and anionic PFOAs. Theor Chem Acc 134, 124 (2015). https://doi.org/10.1007/s00214-015-1725-4

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