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