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

Abstract

In this work, the pure rotational spectrum of the vinoxy radical (CH 2 CHO) has been studied at millimeter and sub-millimeter wavelengths (110−860 GHz). CH 2 CHO was produced by Habstraction from acetaldehyde (CH 3 CHO) 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 CH 2 CHO 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 CH 2 CHO 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.