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Register a new userSpace and laboratory observation of the deuterated cyanomethyl radical HDCCN
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Our observations of TMC-1 with the Yebes 40 m radio telescope in the 31.0-50.3 GHz range allowed us to detect a group of unidentified lines, showing a complex line pattern indicative of an open-shell species. {}The observed frequencies of these lines and the similarity of the spectral pattern with that of the 2$_{0,2}$-1$_{0,1}$ rotational transition of H$_2$CCN indicate that the lines arise from the deuterated cyanomethyl radical, HDCCN. Using Fourier transform microwave spectroscopy experiments combined with electric discharges, we succeeded in producing the radical HDCCN in the laboratory and observed its 1$_{0,1}$-0$_{0,0}$ and 2$_{0,2}$-1$_{0,1}$ rotational transitions. From our observations and assuming a rotational temperature of 5 K, we derive an abundance ratio H$_2$CCN/HDCCN=20$pm$4. The high abundance of the deuterated form of H$_2$CCN is well accounted for by a standard gas-phase model, in which deuteration is driven by deuteron transfer from the H$_2$D$^+$ molecular ion.
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The deuteration mechanism of molecules in the interstellar medium (ISM) is still being debated. Observations of deuterium-bearing species in several astronomical sources represent a powerful tool to improve our understanding of the interstellar chemistry. The doubly deuterated form of the astrophysically interesting Amidogen radical could be a target of detection in space. In this work, the rotational spectrum of the ND$_{2}$ radical in its ground vibrational and electronic $X^{2}B_{1}$ states has been investigated between 588 and 1131 GHz using a frequency modulation millimeter/submillimeter-wave spectrometer. The ND$_{2}$ has been produced in a free-space glass absorption cell by discharging a mixture of ND$_{3}$ and Ar. Sixty-four new transition frequencies involving $J$ values from 2 to 5 and $K_{a}$ values from 0 to 4 have been measured. A global analysis including all the previous field-free pure rotational data has been performed, allowing for a more precise determination of a very large number of spectroscopic parameters. Accurate predictions of rotational transition frequencies of ND$_{2}$ are now available from a few GHz up to several THz.
We report the detection in TMC-1 of the protonated form of C3S. The discovery of the cation HC3S+ was carried through the observation of four harmonically related lines in the Q band using the Yebes 40m radiotelescope, and is supported by accurate ab initio calculations and laboratory measurements of its rotational spectrum. We derive a column density N(HC3S+) = (2.0 +/- 0.5)e11 cm-2, which translates to an abundance ratio C3S/HC3S+ of 65 +/- 20. This ratio is comparable to the CS/HCS+ ratio (35 +/- 8) and is a factor of about ten larger than the C3O/HC3O+ ratio previously found in the same source. However, the abundance ratio HC3O+/HC3S+ is 1.0 +/- 0.5, while C3O/C3S is just 0.11. We also searched for protonated C2S in TMC-1, based on ab initio calculations of its spectroscopic parameters, and derive a 3sigma upper limit of N(HC2S+) < 9e11 cm-2 and a C2S/HC2S+ > 60. The observational results are compared with a state-of-the-art gas-phase chemical model and conclude that HC3S+ is mostly formed through several pathways: proton transfer to C3S, reaction of S+ with c-C3H2, and reaction between neutral atomic sulfur and the ion C3H3+.
The thiophenoxy radical (C6H5S) is a species of possible astrophysical interest due to an electronic transition in a 5000 A region. The B <-- X electronic transition of this radical in the discharge of thiophenol was measured using a cavity ring-down spectrometer. The optical absorption spectrum of this transition was obtained in the range covering from the origin band (0-0) to a frequency of 1750 cm-1. The vibronic bands in the 400-1700 cm-1 region are stronger than the origin band, suggesting structural difference between the ground and excited electronic states. The prominent progression was assigned to the 6a symmetric in-plane CCC bending mode starting from the 6b10 forbidden band. Band origins of individual bands were determined by analysis of the rotational profiles. Although these vibronic bands were not found in optical spectra of diffuse clouds, the upper limits of the column densities for the thiophenoxy radical in the diffuse clouds toward HD 183143 and HD 204827 were evaluated to be 4 x 10^13 cm-2.
Using the Yebes 40m and IRAM 30m radiotelescopes, we detected two series of harmonically related lines in space that can be fitted to a symmetric rotor. The lines have been seen towards the cold dense cores TMC-1, L483, L1527, and L1544. High level of theory ab initio calculations indicate that the best possible candidate is the acetyl cation, CH3CO+, which is the most stable product resulting from the protonation of ketene. We have produced this species in the laboratory and observed its rotational transitions Ju = 10 up to Ju = 27. Hence, we report the discovery of CH3CO+ in space based on our observations, theoretical calculations, and laboratory experiments. The derived rotational and distortion constants allow us to predict the spectrum of CH3CO+ with high accuracy up to 500 GHz. We derive an abundance ratio N(H2CCO)/N(CH3CO+) = 44. The high abundance of the protonated form of H2CCO is due to the high proton affinity of the neutral species. The other isomer, H2CCOH+, is found to be 178.9 kJ/mol above CH3CO+. The observed intensity ratio between the K=0 and K=1 lines, 2.2, strongly suggests that the A and E symmetry states have suffered interconversion processes due to collisions with H and/or H2, or during their formation through the reaction of H3+ with H2CCO.
Glycolaldehyde, a sugar-related interstellar prebiotic molecule, has recently been detected in two star-forming regions, Sgr B2(N) and G31.41+0.31. The detection of this new species increased the list of complex organic molecules detected in the interstellar medium (ISM) and adds another level to the chemical complexity present in space. Besides, this kind of organic molecule is important because it is directly linked to the origin of life. For many years, astronomers have been struggling to understand the origin of this high chemical complexity in the ISM. The study of deuteration may provide crucial hints. In this context, we have measured the spectra of deuterated isotopologues of glycolaldehyde in the laboratory: the three monodeuterated ones (CH2OD-CHO, CHDOH-CHO and CH2OH-CDO) and one dideuterated derivative (CHDOH-CDO) in the ground vibrational state. Previous laboratory work on the D-isotopologues of glycolaldehyde was restricted to less than 26 GHz. We used a solidstate submillimeter-wave spectrometer in Lille with an accuracy for isolated lines better than 30 kHz to acquire new spectroscopic data between 150 and 630 GHz and employed the ASFIT and SPCAT programs for analysis. We measured around 900 new lines for each isotopologue and determined spectroscopic parameters. This allows an accurate prediction in the ALMA range up to 850 GHz. This treatment meets the needs for a first astrophysical research, for which we provide an appropriate set of predictions.
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