Details

Autor(en) / Beteiligte

• Coudert, L. H.
• Chitarra, O.
• Spaniol, J.-T.
• Loison, J.-C.
• Martin-Drumel, M.-A.
• Pirali, O.

Titel

Tunneling motion and splitting in the CH2OH radical: (Sub-)millimeter wave spectrum analysis

Ist Teil von

• The Journal of chemical physics, 2022-06, Vol.156 (24), p.244301-244301

Ort / Verlag

Melville: American Institute of Physics

Erscheinungsjahr

2022

Quelle

American Institute of Physics (AIP) Journals

Beschreibungen/Notizen

• The (sub-)millimeter wave spectrum of the non-rigid CH2OH radical is investigated both experimentally and theoretically. Ab initio calculations are carried out to quantitatively characterize its potential energy surface as a function of the two large amplitude ∠H1COH and ∠H2COH dihedral angles. It is shown that the radical displays a large amplitude torsional-like motion of its CH2 group with respect to the OH group. The rotation–torsion levels computed with the help of a 4D Hamiltonian accounting for this torsional-like motion and for the overall rotation exhibit a tunneling splitting, in agreement with recent experimental investigations, and a strong rotational dependence of this tunneling splitting on the rotational quantum number Ka due to the rotation–torsion Coriolis coupling. Based on an internal axis method approach, a fitting Hamiltonian accounting for tunneling effects and for the fine and hyperfine structure is built and applied to the fitting of the new (sub)-millimeter wave transitions measured in this work along with previously available high-resolution data. 778 frequencies and wavenumbers are reproduced with a unitless standard deviation of 0.79 using 27 parameters. The N = 0 tunneling splitting, which could not be determined unambiguously in the previous high-resolution investigations, is determined based on its rotational dependence.