@article{10272/21708,
year = {2022},
url = {https://hdl.handle.net/10272/21708},
abstract = {Two ketones of atmospheric interest, methyl glyoxal and methyl vinyl ketone,
are studied using explicitly correlated coupled cluster theory and core-valence correlationconsistent
basis sets. The work focuses on the far-infrared region. At the employed level of
theory, the rotational constants can be determined to within a few megahertz of the
experimental data. Both molecules present two conformers, trans/cis and antiperiplanar (Ap)/
synperiplanar (Sp), respectively. trans-Methyl glyoxal and Ap-methyl vinyl ketone are the
preferred structures. cis-Methyl glyoxal is a secondary minimum of very low stability, which
justifies the unavailability of experimental data in this form. In methyl vinyl ketone, the two conformers are almost isoenergetic, but
the interconversion implies a relatively high torsional barrier of 1798 cm-1. A very low methyl torsional barrier was estimated for
trans-methyl glyoxal (V3 = 273.6 cm-1). Barriers of 429.6 and 380.7 cm-1 were computed for Ap- and Sp-methyl vinyl ketone.
Vibrational second-order perturbation theory was applied to determine the rovibrational parameters. The far-infrared region was
explored using a variational procedure of reduced dimensionality. For trans-methyl glyoxal, the ground vibrational state was
estimated to split by 0.067 cm-1, and the two low excited energy levels (1 0) and (0 1) were found to lie at 89.588 cm-1/88.683
cm-1 (A2/E) and 124.636 cm-1/123.785 cm-1 (A2/E). For Ap- and Sp-methyl vinyl ketone, the ground vibrational state splittings
were estimated to be 0.008 and 0.017 cm-1, respectively.},
organization = {This project received funding from the European Union’s
Horizon 2020 Research and Innovation Programme under
Marie Skłodowska-Curie Grant Agreement 872081. The
authors acknowledge the National Plan for Science, Technology
and Innovation (MAARIFAH), King Abdulaziz City for Science
and Technology, Kingdom of Saudi Arabia (Award 0061-001-
01-17-2) and the Ministerio de Ciencia, Innovación y
Universidades of Spain (Grants EIN2019-103072, PID2020-
112887GB-I00, PID2019-104002GB-C21, and ERDF A Way of
Making Europe, by the European Union Next Generation EU/
PRTR). The authors acknowledge CTI (CSIC) and CESGA
and the Red Española de Computación for Grants AECT-2020-
2-0008 and RES-AECT-2020-3-0011 for computing facilities.},
publisher = {American Chemical Society},
title = {Theoretical Spectroscopic Study of Two Ketones of Atmospheric Interest: Methyl Glyoxal (CH3COCHO) and Methyl Vinyl Ketone (CH3COCH═CH2)},
doi = {10.1021/acs.jpca.2c05653},
author = {Toumi, Insaf and Dalbouha, Samira and Al-Mogren, Muneerah Mogren and Yazidi, Ounaies and Jaïdane, Nejm-Eddine and Carvajal Zaera, Miguel and Senent, María Luisa},
}