High-Resolution Spectroscopic Investigation of the CH2CHO Radical in the Sub-Millimeter Region

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-01, Vol.128 (2), p.370-377
• Main Authors: Chahbazian, Rosemonde, Martin-Drumel, Marie-Aline, Pirali, Olivier
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.3c06326

In this work, the pure rotational spectrum of the vinoxy radical (CH2CHO) has been studied at millimeter and sub-millimeter wavelengths (110–860 GHz). CH2CHO was produced by H-abstraction from acetaldehyde (CH3CHO) using atomic fluorine in a double-pass absorption cell at room temperature. A Zeeman-modulation spectrometer, in which an external magnetic field generated inside the absorption cell is amplitude-modulated, was used to record the pure rotational transitions of the radical. The recorded spectra are devoid of signals from closed-shell species, allowing for relatively fast acquisitions over wide spectral windows. Transitions involving values of the rotational quantum numbers N″ and K a ″ up to 41 and 18, respectively, were measured and combined with all available high-resolution literature data (both pure rotation and ground-state combination differences from ro-vibration) to greatly improve the modeling of the CH2CHO spectrum. The combined experimental line list is fit using a semirigid rotor Hamiltonian, and the results are compared to quantum chemical calculations. This laboratory study provides the spectroscopic information needed to search for CH2CHO in various interstellar environments, from cold (e.g., typically 10 K for dense molecular clouds) to warm (e.g., ∼200 K for hot corinos) objects.