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The puzzling structure and bonding of the methanol radical cation
Linköping University, Department of Physics, Chemistry and Biology, Theoretical Physics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-7648-6903
Univ Antioquia UdeA, Colombia.
Univ Antioquia UdeA, Colombia.
2025 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 162, no 11, article id 114306Article in journal (Refereed) Published
Abstract [en]

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-C-O-H bonds, in which the C-H and O-H bonds eclipse each other, is a three-fold global minimum in the potential energy surface for internal rotation of the O-H bond. We show that vicinal hyperconjugation between the orbitals in the C-H bonds and in the oxygen atom is responsible for this puzzling conformational preference. The transition state for the rotation yields an approximate to 0.6 kcal/mol rotational barrier, which matches the thermal energy at room conditions and, therefore, renders the O-H 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.

Place, publisher, year, edition, pages
AIP Publishing , 2025. Vol. 162, no 11, article id 114306
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-212720DOI: 10.1063/5.0250493ISI: 001448184700011PubMedID: 40105134Scopus ID: 2-s2.0-105000418758OAI: oai:DiVA.org:liu-212720DiVA, id: diva2:1948972
Note

Funding Agencies|Universidad de Antioquiahttps://doi.org/10.13039/501100005278; Universidad de Antioquia via the Estrategia para la sostenibilidad

Available from: 2025-04-01 Created: 2025-04-01 Last updated: 2025-04-01

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