Millimeter wave spectroscopy of propynal isotopologues and structure determination

Autor: Evan G. Robertson, Mahmut Ruzi, Don McNaughton, Laurent Margulès, Roman A. Motiyenko, Jean-Claude Guillemin
Přispěvatelé: La Trobe University, Erciyes University, Monash university, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Computational Infrastructure, NCI: k02, La Trobe University, LTU, Centre National d’Etudes Spatiales, CNES, Commissariat à l'Énergie Atomique et aux Énergies Alternatives, CEA
Rok vydání: 2023
Předmět:
Zdroj: Journal of Molecular Spectroscopy
Journal of Molecular Spectroscopy, 2023, 394, pp.111786. ⟨10.1016/j.jms.2023.111786⟩
ISSN: 0022-2852
1096-083X
DOI: 10.1016/j.jms.2023.111786
Popis: International audience; Rotational transitions of propynal (HCCCHO) have been measured in the 150–900 GHz region by millimeter wave spectroscopy and in the far infrared region by high resolution FTIR spectroscopy using a synchrotron source. For the parent isotopologue, assignment of MMW transitions up to very high quantum numbers (J = 100, Ka = 25) reveals evidence of extensive perturbations in the ground vibrational state due to Fermi-asymmetry resonance with an excited vibrational state. A fit to nearly 3000 ground state transitions yields effective constants that are suitable for describing relatively unperturbed rotational levels up to Ka = 13. Over 1000 transitions were assigned and fitted for each singly substituted 13C species and nearly 400 transitions for the 18O variant. Re-analysis of literature data on deuterated species, aided by centrifugal distortion constants from hybrid density functional theory calculations at the B2PLYP/aug-cc-pVTZ level, provides a further set of rotational constants. This allows determination of a Rm(2) structure for propynal with the following geometry: r(C≡C) = 1.2066(15), r(C[sbnd]C) = 1.4486(14), r(CO) = 1.2087(10), r(C­H ald) = 1.1069(8), r(C­H acet) = 1.0578(13), θ(CCC) = 176.71(22), θ(OCC) = 123.23(7), θ(HCC ald) = 114.43(31), θ(HCC acet) = 178.45(16). A new Rs structure was also derived.
Databáze: OpenAIRE
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