{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,7,30]],"date-time":"2025-07-30T11:26:45Z","timestamp":1753874805647,"version":"3.41.2"},"reference-count":48,"publisher":"AIP Publishing","issue":"11","funder":[{"DOI":"10.13039\/501100005278","name":"Universidad de Antioquia","doi-asserted-by":"publisher","award":["Estrategia para la sostenibilidad"],"award-info":[{"award-number":["Estrategia para la sostenibilidad"]}],"id":[{"id":"10.13039\/501100005278","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2025,3,21]]},"abstract":"<jats:p>Electron spin resonance indicates that the unpaired electron in the methanol radical cation is delocalized, however, the molecular geometry has not been experimentally resolved. In this work, high level, state-of-the-art computations at the finite temperature density functional theory and highly correlated CCSD(T) levels indicate that a syn-periplanar conformation of the H\u2013C\u2013O\u2013H bonds, in which the C\u2013H and O\u2013H bonds eclipse each other, is a three-fold global minimum in the potential energy surface for internal rotation of the O\u2013H bond. We show that vicinal hyperconjugation between the orbitals in the C\u2013H bonds and in the oxygen atom is responsible for this puzzling conformational preference. The transition state for the rotation yields an \u22480.6 kcal\/mol rotational barrier, which matches the thermal energy at room conditions and, therefore, renders the O\u2013H bond a free rotor. The molecular wave function has a moderate multireference character with the oxygen atom acting as the preferred spot for static correlation.<\/jats:p>","DOI":"10.1063\/5.0250493","type":"journal-article","created":{"date-parts":[[2025,3,19]],"date-time":"2025-03-19T10:31:05Z","timestamp":1742380265000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["The puzzling structure and bonding of the methanol radical cation"],"prefix":"10.1063","volume":"162","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7648-6903","authenticated-orcid":false,"given":"Santiago","family":"G\u00f3mez","sequence":"first","affiliation":[{"name":"Department of Physics, Chemistry and Biology (IFM), Link\u00f6ping University 1 , Link\u00f6ping 58183,","place":["Sweden"]},{"name":"Instituto de Qu\u00edmica, Universidad de Antioquia UdeA 2 , Calle 70 No. 52-21, Medell\u00edn 050010,","place":["Colombia"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-0332-1066","authenticated-orcid":false,"given":"Jhoan","family":"Londo\u00f1o\u2013Restrepo","sequence":"additional","affiliation":[{"name":"Instituto de F\u00edsica, Universidad de Antioquia UdeA 3 , Calle 70 No. 52-21, Medell\u00edn,","place":["Colombia"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7866-7791","authenticated-orcid":false,"given":"Albeiro","family":"Restrepo","sequence":"additional","affiliation":[{"name":"Instituto de Qu\u00edmica, Universidad de Antioquia UdeA 2 , Calle 70 No. 52-21, Medell\u00edn 050010,","place":["Colombia"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2025,3,19]]},"reference":[{"key":"2025031910304916400_c1","doi-asserted-by":"publisher","DOI":"10.1002\/14356007.a16_465.pub3","article-title":"Methanol","volume-title":"Ullmann's Encyclopedia of Industrial Chemistry","year":"2012"},{"key":"2025031910304916400_c2","doi-asserted-by":"publisher","first-page":"1217","DOI":"10.1016\/j.rser.2018.06.058","article-title":"Renewable methanol as a fuel for the shipping industry","volume":"94","year":"2018","journal-title":"Renewable Sustainable Energy Rev."},{"key":"2025031910304916400_c3","doi-asserted-by":"publisher","first-page":"42","DOI":"10.1016\/0022-2852(84)90285-6","article-title":"A new analysis and additional measurements of the millimeter and submillimeter spectrum of methanol","volume":"108","year":"1984","journal-title":"J.\u00a0Mol. 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