RT Journal Article
T1 Theoretical Spectroscopic Study of Two Ketones of Atmospheric Interest: Methyl Glyoxal (CH3COCHO) and Methyl Vinyl Ketone (CH3COCH═CH2)
A1 Toumi, Insaf
A1 Dalbouha, Samira
A1 Al-Mogren, Muneerah Mogren
A1 Yazidi, Ounaies
A1 Jaïdane, Nejm-Eddine
A1 Carvajal Zaera, Miguel
A1 Senent, María Luisa
AB Two ketones of atmospheric interest, methyl glyoxal and methyl vinyl ketone,are studied using explicitly correlated coupled cluster theory and core-valence correlationconsistentbasis sets. The work focuses on the far-infrared region. At the employed level oftheory, the rotational constants can be determined to within a few megahertz of theexperimental data. Both molecules present two conformers, trans/cis and antiperiplanar (Ap)/synperiplanar (Sp), respectively. trans-Methyl glyoxal and Ap-methyl vinyl ketone are thepreferred structures. cis-Methyl glyoxal is a secondary minimum of very low stability, whichjustifies the unavailability of experimental data in this form. In methyl vinyl ketone, the two conformers are almost isoenergetic, butthe interconversion implies a relatively high torsional barrier of 1798 cm-1. A very low methyl torsional barrier was estimated fortrans-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 wasexplored using a variational procedure of reduced dimensionality. For trans-methyl glyoxal, the ground vibrational state wasestimated 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-1/88.683cm-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 splittingswere estimated to be 0.008 and 0.017 cm-1, respectively.
PB American Chemical Society
SN 1089-5639
SN 1520-5215 (electrónico)
YR 2022
FD 2022
LK https://hdl.handle.net/10272/21708
UL https://hdl.handle.net/10272/21708
LA eng
NO Toumi, I., Dalbouha, S., Al-Mogren, M. M., Yazidi, O., Jaïdane, N.-E., Carvajal, M., & Senent, M. L. (2022). Theoretical Spectroscopic Study of Two Ketones of Atmospheric Interest: Methyl Glyoxal (CH3COCHO) and Methyl Vinyl Ketone (CH3COCH═CH2). In The Journal of Physical Chemistry A (Vol. 126, Issue 40, pp. 7230–7241). American Chemical Society (ACS). https://doi.org/10.1021/acs.jpca.2c05653
NO This project received funding from the European Union’sHorizon 2020 Research and Innovation Programme underMarie Skłodowska-Curie Grant Agreement 872081. Theauthors acknowledge the National Plan for Science, Technologyand Innovation (MAARIFAH), King Abdulaziz City for Scienceand Technology, Kingdom of Saudi Arabia (Award 0061-001-01-17-2) and the Ministerio de Ciencia, Innovación yUniversidades of Spain (Grants EIN2019-103072, PID2020-112887GB-I00, PID2019-104002GB-C21, and ERDF A Way ofMaking Europe, by the European Union Next Generation EU/PRTR). The authors acknowledge CTI (CSIC) and CESGAand the Red Española de Computación for Grants AECT-2020-2-0008 and RES-AECT-2020-3-0011 for computing facilities.
DS Repositorio Institucional de la Universidad de Huelva
RD 31 may 2026