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In addition to the persistent nature of PFAS, the structural and functional diversity in PFAS creates a unique challenge in identification and remediation. Their identification is further complicated by the absence of standards for many PFAS. This work is aimed at developing a protocol for computing and establishing accurate <jats:sup>19<\/jats:sup>F NMR chemical shifts for PFAS using density functional theory (DFT), which can aid in the identification of PFAS. The impact of solvation and basis sets was evaluated by comparing the computed data with the experimental measurements. Results showed the addition of dispersion corrections in the methodology improve the accuracy of calculated NMR parameters within 4\u00a0ppm of the experimental values. Adding a second diffuse function and additional polarization did not improve the accuracy, likely because of the electronegativity of fluorine which does not allow the electron density of fluorine atoms to be polarized. The inclusion of various implicit solvation (DMSO, chloroform, and water) yielded negligible differences in accuracy, and were overall less accurate than the gas phase calculations. The most accurate methodology was then applied to more environmentally relevant PFAS, and the impact of helical nature on the NMR signatures was evaluated. The implication of this work is to be able to improve the identification of structurally diverse PFAS using the <jats:sup>19<\/jats:sup>F NMR.<\/jats:p>","DOI":"10.1002\/jcc.26939","type":"journal-article","created":{"date-parts":[[2022,6,6]],"date-time":"2022-06-06T12:10:35Z","timestamp":1654517435000},"page":"1355-1361","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Computational protocol for predicting <scp><sup>19<\/sup>F NMR<\/scp> chemical shifts for <scp>PFAS<\/scp> and connection to <scp>PFAS<\/scp> structure"],"prefix":"10.1002","volume":"43","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8972-3437","authenticated-orcid":false,"given":"Maleigh","family":"Mifkovic","sequence":"first","affiliation":[{"name":"Department of Chemistry Colorado School of Mines  Golden Colorado USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5532-2598","authenticated-orcid":false,"given":"Jessica","family":"Pauling","sequence":"additional","affiliation":[{"name":"Department of Chemistry Colorado School of Mines  Golden Colorado USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5849-8919","authenticated-orcid":false,"given":"Shubham","family":"Vyas","sequence":"additional","affiliation":[{"name":"Department of Chemistry Colorado School of Mines  Golden Colorado USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,6,6]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/es991359u"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp801081y"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.3390\/ijerph17218117"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.est.6b04806"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemosphere.2020.127659"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.envint.2019.03.002"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41370-018-0094-1"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/es022253t"},{"key":"e_1_2_7_10_1","unstructured":"Lifetime Health Advisories and Health Effects Support Documents for Perfluorooctanoic Acid and Perfluorooctane Sulfonate; Notice of Availability 2016 81(101) 33250 Fed. 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