Tunneling motion and splitting in the CH$_2$OH radical: (Sub-)millimeter wave spectrum analysis

Abstract

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>/it> = 0 tunneling splitting, which could not be determined unambiguously in the previous high-resolution investigations, is determined based on its rotational dependence. .

Publication
The Journal of Chemical Physics
Olivia Chitarra
Olivia Chitarra
PhD student

PhD student at Institut des Sciences Moléculaires d’Orsay (ISMO) under the direction of Olivier Pirali and Marie-Aline Martin-Drumel.

Jean-Thibaut Spaniol
Jean-Thibaut Spaniol
Master Student

Master 2 student with a passion for teaching that overpassed his love for spectroscopy.

Marie-Aline Martin-Drumel
Marie-Aline Martin-Drumel
Researcher

My research interests focus on molecular spectroscopy of stable molecules and reactive species, and its applications for astrophysics and physical-chemistry.

Olivier Pirali
Olivier Pirali
Director of Research

My research interests includes high resolution molecular spectroscopy, laboratory astrophysics, and THz generation.