Detection of deuterated methylcyanoacetylene, CH2DC3N, in TMC-1.

We report the first detection in space of the single deuterated isotopologue of methylcyanoacetylene, CH2DC3N. A total of fifteen rotational transitions, with J = 8-12 and Ka = 0 and 1, were identified for this species in TMC-1 in the 31.0-50.4 GHz range using the Yebes 40m radio telescope. The observed frequencies were used to derive for the first time the spectroscopic parameters of this deuterated isotopologue. We derive a column density of (8.0 ± 0.4) × 1010 cm-2. The abundance ratio between CH3C3N and CH2DC3N is ∼22. We also theoretically computed the principal spectroscopic constants of 13C isotopologues of CH3C3N and CH3C4H and those of the deuterated isotopologues of CH3C4H for which we could expect a similar degree of deuteration enhancement. However, we have not detected either CH2DC4H nor CH3C4D nor any 13C isotopologue. The different observed deuterium ratios in TMC-1 are reasonably accounted for by a gas phase chemical model where the low temperature conditions favor deuteron transfer through reactions with H2D+.

A study of C4H3N isomers in TMC-1: line by line detection of HCCCH2CN.

We present Yebes 40m telescope observations of the three most stable C4H3N isomers towards the cyanopolyyne peak of TMC-1. We have detected 13 transitions from CH3C3N (A and E species), 16 lines from CH2CCHCN, and 27 lines (a-type and b-type) from HCCCH2CN. We thus provide a robust confirmation of the detection of HCCCH2CN and CH2CCHCN in space. We have constructed rotational diagrams for the three species, and obtained rotational temperatures between 4-8 K and similar column densities for the three isomers, in the range (1.5-3)×1012 cm-2. Our chemical model provides abundances of the order of the observed ones, although it overestimates the abundance of CH3CCCN and underestimates that of HCCCH2CN. The similarity of the observed abundances of the three isomers suggests a common origin, most probably involving reactions of the radical CN with the unsaturated hydrocarbons methyl acetylene and allene. Studies of reaction kinetics at low temperature and further observations of these molecules in different astronomical sources are needed to draw a clear picture of the chemistry of C4H3N isomers in space.

Space and laboratory discovery of HC3 S.

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) × 1011 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 3σ upper limit of N(HC2S+)≤ 9×1011 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 C3H+ 3.

Rotational spectroscopic study and astronomical search for propiolamide in Sgr B2(N).

CONTEXT: For all the amides detected in the interstellar medium (ISM), the corresponding nitriles or isonitriles have also been detected in the ISM, some of which have relatively high abundances. Among the abundant nitriles for which the corresponding amide has not yet been detected is cyanoacetylene (HCCCN), whose amide counterpart is propiolamide (HCCC(O)NH2). AIMS: With the aim of supporting searches for this amide in the ISM, we provide a complete rotational study of propiolamide from 6 GHz to 440 GHz. METHODS: Time-domain Fourier transform microwave (FTMW) spectroscopy under supersonic expansion conditions between 6 GHz and 18 GHz was used to accurately measure and analyze ground-state rotational transitions with resolved hyperfine structure arising from nuclear quadrupole coupling interactions of the 14N nucleus. We combined this technique with the frequency-domain room-temperature millimeter wave and submillimeter wave spectroscopies from 75 GHz to 440 GHz in order to record and assign the rotational spectra in the ground state and in the low-lying excited vibrational states. We used the ReMoCA spectral line survey performed with the Atacama Large Millimeter/submillimeter Array toward the star-forming region Sgr B2(N) to search for propiolamide. RESULTS: We identified and measured more than 5500 distinct frequency lines of propiolamide in the laboratory. These lines were fitted using an effective semi-rigid rotor Hamiltonian with nuclear quadrupole coupling interactions taken into consideration. We obtained accurate sets of spectroscopic parameters for the ground state and the three low-lying excited vibrational states. We report the nondetection of propiolamide toward the hot cores Sgr B2(N1S) and Sgr B2(N2). We find that propiolamide is at least 50 and 13 times less abundant than acetamide in Sgr B2(N1S) and Sgr B2(N2), respectively, indicating that the abundance difference between both amides is more pronounced by at least a factor of 8 and 2, respectively, than for their corresponding nitriles. CONCLUSIONS: Although propiolamide has yet to be included in astrochemical modeling networks, the observed upper limit to the ratio of propiolamide to acetamide seems consistent with the ratios of related species as determined from past simulations. The comprehensive spectroscopic data presented in this paper will aid future astronomical searches.

Gas phase Elemental abundances in Molecular cloudS (GEMS) II. On the quest for the sulphur reservoir in molecular clouds: the H2S case.

CONTEXT: Sulphur is one of the most abundant elements in the Universe. Surprisingly, sulphuretted molecules are not as abundant as expected in the interstellar medium and the identity of the main sulphur reservoir is still an open question. AIMS: Our goal is to investigate the H2S chemistry in dark clouds, as this stable molecule is a potential sulphur reservoir. METHODS: Using millimeter observations of CS, SO, H2S, and their isotopologues, we determine the physical conditions and H2S abundances along the cores TMC 1-C, TMC 1-CP, and Barnard 1b. The gas-grain model Nautilus is used to model the sulphur chemistry and explore the impact of photo-desorption and chemical desorption on the H2S abundance. RESULTS: Our modeling shows that chemical desorption is the main source of gas-phase H2S in dark cores. The measured H2S abundance can only be fitted if we assume that the chemical desorption rate decreases by more than a factor of 10 when n H > 2 × 104. This change in the desorption rate is consistent with the formation of thick H2O and CO ice mantles on grain surfaces. The observed SO and H2S abundances are in good agreement with our predictions adopting an undepleted value of the sulphur abundance. However, the CS abundance is overestimated by a factor of 5 - 10. Along the three cores, atomic S is predicted to be the main sulphur reservoir. CONCLUSIONS: The gaseous H2S abundance is well reproduced, assuming undepleted sulphur abundance and chemical desorption as the main source of H2S. The behavior of the observed H2S abundance suggests a changing desorption efficiency, which would probe the snowline in these cold cores. Our model, however, highly overestimates the observed gas-phase CS abundance. Given the uncertainty in the sulphur chemistry, we can only conclude that our data are consistent with a cosmic elemental S abundance with an uncertainty of a factor of 10.

The Spatial Distribution of Complex Organic Molecules in the L1544 Pre-stellar Core.

The detection of complex organic molecules (COMs) toward cold sources such as pre-stellar cores (with T<10 K), has challenged our understanding of the formation processes of COMs in the interstellar medium. Recent modelling on COM chemistry at low temperatures has provided new insight into these processes predicting that COM formation depends strongly on parameters such as visual extinction and the level of CO freeze out. We report deep observations of COMs toward two positions in the L1544 pre-stellar core: the dense, highly-extinguished continuum peak with A V ≥30 mag within the inner 2700 au; and a low-density shell with average A V ~7.5-8 mag located at 4000 au from the core's center and bright in CH3OH. Our observations show that CH3O, CH3OCH3 and CH3CHO are more abundant (by factors ~2-10) toward the low-density shell than toward the continuum peak. Other COMs such as CH3OCHO, c-C3H2O, HCCCHO, CH2CHCN and HCCNC show slight enhancements (by factors ≤3) but the associated uncertainties are large. This suggests that COMs are actively formed and already present in the low-density shells of pre-stellar cores. The modelling of the chemistry of O-bearing COMs in L1544 indicates that these species are enhanced in this shell because i) CO starts freezing out onto dust grains driving an active surface chemistry; ii) the visual extinction is sufficiently high to prevent the UV photo-dissociation of COMs by the external interstellar radiation field; and iii) the density is still moderate to prevent severe depletion of COMs onto grains.

The first CO+ image: I. Probing the HI/H2 layer around the ultracompact HII region Mon R2.

The CO+ reactive ion is thought to be a tracer of the boundary between a HII region and the hot molecular gas. In this study, we present the spatial distribution of the CO+ rotational emission toward the Mon R2 star-forming region. The CO+ emission presents a clumpy ring-like morphology, arising from a narrow dense layer around the HII region. We compare the CO+ distribution with other species present in photon-dominated regions (PDR), such as [CII] 158 µm, H2 S(3) rotational line at 9.3 µm, polycyclic aromatic hydrocarbons (PAHs) and HCO+. We find that the CO+ emission is spatially coincident with the PAHs and [CII] emission. This confirms that the CO+ emission arises from a narrow dense layer of the HI/H2 interface. We have determined the CO+ fractional abundance, relative to C+ toward three positions. The abundances range from 0.1 to 1.9 ×10-10 and are in good agreement with previous chemical model, which predicts that the production of CO+ in PDRs only occurs in dense regions with high UV fields. The CO+ linewidth is larger than those found in molecular gas tracers, and their central velocity are blue-shifted with respect to the molecular gas velocity. We interpret this as a hint that the CO+ is probing photo-evaporating clump surfaces.