Accurate rest frequencies for propargylamine in the ground and low-lying vibrational states

Abstract

Context. To date, several complex organic molecules have been detected in the interstellar medium, and they have been suggested as precursors of biologically important species. Propargylamine (HC ≡C−CH2−NH2) is structurally similar to a number of other organic molecules which have already been identified by radioastronomy, making it a good candidate for astrophysical detection. Aims. This work provides accurate rest frequencies of propargylamine, from the centimeter-wave to the submillimeter-wave region, useful to facilitate the detection of this molecule in the interstellar medium. Methods. An extensive laboratory study of the rotational spectrum of propargylamine has been performed using a pulsed-jet Fourier Transform Microwave (FTMW) spectrometer (7–19 GHz frequency range) and a frequency modulation microwave spectrometer (75–560 GHz). Several hundred rotational transitions of propargylamine were recorded in the ground and three lowest excited vibrational states. The experiments were supported by high-level ab initio computations, mainly employed to characterize the vibrational state structure and to predict spectroscopic parameters unknown prior to this study. Results. The measured transition frequencies yielded accurate rotational constants and the complete sets of quartic and sextic centrifugal distortion constants for propargylamine in its vibrational ground state. 14N-nuclear quadrupole coupling constants were also determined. Rotational and quartic centrifugal distortion constants were also obtained for the low-lying excited states v13 = 1 (A′), v20 = 1 (A″), and v21 = 1 (A″). The a-type Coriolis resonance which couples the v13 = 1 and v21 = 1 levels was analyzed. Conclusions. The determined spectroscopic constants allowed for the compilation of a dataset of highly accurate rest frequencies for astrophysical purposes in the millimeter and submillimeter regions with 1σ uncertainties that are smaller than 0.050 MHz, corresponding to 0.03 km s−1 at 500 GHz in radial equivalent velocity.

A twist on the reaction of the CN radical with methylamine in the interstellar medium: new hints from a state-of-the-art quantum-chemical study

“…According to the literature on this topic (see, e.g., Puzzarini et al (2008 (2018)), the rotational constants are expected to have an accuracy, in relative terms, of about 0.1%, while the uncertainties affecting centrifugal-distortion constants and hyperfine parameters should not exceed 1-2%. While these computational results do not have the required accuracy to directly guide astronomical searches, they can surely support laboratory experiments and their analysis (see, e.g., ; Cazzoli et al (2014); Degli Esposti et al (2018)). CH 2 NH 2 and CH 3 NH being radical species, the first challenge for a laboratory investigation is their in situ production.…”

Propargylimine in the laboratory and in space: millimetre-wave spectroscopy and its first detection in the ISM

“…Employing a similar composite approach (see e.g. Barone et al 2015;Pietropolli Charmet et al 2017a;Degli Esposti et al 2018) the best-estimate values of the quadratic force fields were derived. Cubic and semi-diagonal quartic force constants, computed at different levels of theory, were employed for the vibrational corrections to the equilibrium rotational constants, for the anharmonic corrections to the harmonic frequencies, and for determining the sextic centrifugal distortion constants.…”

Rich Collection of n-Propylamine and Isopropylamine Conformers: Rotational Fingerprints and State-of-the-Art Quantum Chemical Investigation

“…Second, other small amines have been suggested to exist in both trans and gauche forms by ab initio calculations or low-resolution experiments (e.g., see refs ( 43 , 44 ) for aminoacetonitrile and propargylamine), but only their trans forms (i.e., the most stable ones) have been revealed by high-resolution molecular spectroscopy. 45 , 46 …”