@misc{10481/77843,
year = {2022},
month = {9},
url = {https://hdl.handle.net/10481/77843},
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 = {European Commission	872081},
organization = {National Plan for Science, Technology and Innovation (MAARIFAH), King Abdulaziz City for Science and Technology, Kingdom of Saudi Arabia	0061-00101-17-2},
organization = {Spanish Government	EIN2019-103072	
PID2020112887GB-I00	
PID2019-104002GB-C21},
organization = {ERDF A Way of Making Europe		
European Union Next Generation EU/PRTR},
organization = {CTI (CSIC)},
organization = {CESGA},
organization = {Red Espanola de Computacion	AECT-20202-0008	
RES-AECT-2020-3-0011},
publisher = {American Chemical Society},
title = {Theoretical Spectrscopic 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 Carvajal Rodríguez, Miguel Ángel},
}