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.
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28 June 2022
Research Article|
June 23 2022
Tunneling motion and splitting in the CH2OH radical: (Sub-)millimeter wave spectrum analysis
L. H. Coudert
;
L. H. Coudert
a)
(Formal analysis, Software, Writing – original draft, Writing – review and editing)
1
Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d’Orsay
, 91405 Orsay, France
a)Author to whom correspondence should be addressed: [email protected]
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O. Chitarra
;
O. Chitarra
(Investigation, Resources, Writing – original draft, Writing – review and editing)
1
Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d’Orsay
, 91405 Orsay, France
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J.-T. Spaniol
;
J.-T. Spaniol
(Validation, Writing – original draft, Writing – review and editing)
1
Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d’Orsay
, 91405 Orsay, France
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J.-C. Loison
;
J.-C. Loison
(Data curation, Investigation, Methodology, Resources, Writing – original draft, Writing – review and editing)
2
Institut des Sciences Moléculaires, UMR 5255 CNRS - Université de Bordeaux
, Bât. A12, 351 Cours de la Libération, 33405 Talence Cedex, France
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M.-A. Martin-Drumel
;
M.-A. Martin-Drumel
(Data curation, Investigation, Validation, Writing – original draft, Writing – review and editing)
1
Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d’Orsay
, 91405 Orsay, France
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O. Pirali
O. Pirali
(Conceptualization, Data curation, Methodology, Writing – original draft, Writing – review and editing)
1
Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d’Orsay
, 91405 Orsay, France
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a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 156, 244301 (2022)
Article history
Received:
April 09 2022
Accepted:
June 01 2022
Citation
L. H. Coudert, O. Chitarra, J.-T. Spaniol, J.-C. Loison, M.-A. Martin-Drumel, O. Pirali; Tunneling motion and splitting in the CH2OH radical: (Sub-)millimeter wave spectrum analysis. J. Chem. Phys. 28 June 2022; 156 (24): 244301. https://doi.org/10.1063/5.0095242
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