We report the first identification in space of H2NC, a high-energy isomer of H2CN that has been largely ignored in chemical and astrochemical studies. The observation of various unidentified lines ...around 72.2 GHz in the cold dark cloud L483 motivated the search and successful detection of additional groups of lines in harmonic relation. Following an exhaustive high-level ab initio screening of possible carriers, we confidently assign the unidentified lines to H2NC based on the good agreement between the astronomical and theoretical spectroscopic parameters alongside sound spectroscopic and astrochemical arguments. The observed frequencies are used to precisely characterize the rotational spectrum of H2NC. This species is also detected in the cold dark cloud B1-b and the z = 0.89 galaxy in front of the quasar PKS 1830−211. We derive H2NC/H2CN abundance ratios ~1 in L483 and B1-b and 0.27 toward PKS 1830−211. Neither H2NC nor H2CN are detected in the dark cloud TMC-1, which seriously undermines the previous identification of H2CN in this source. We suggest that the H2NC/H2CN ratio behaves as the HNC/HCN ratio, with values close to one in cold dense clouds and below one in diffuse clouds. The reactions N + CH3 and C + NH3 emerge as strong candidates for the production of H2NC in interstellar clouds. Further studies on these two reactions are needed to evaluate the yield of H2NC. Due to the small number of atoms involved, it should be feasible to constrain the chemistry behind H2NC and H2CN, just as has been done for HNC and HCN, as this could allow for the H2NC/H2CN ratio to be applied as a probe of chemical or physical conditions of the host clouds.
We report the first detection in space of the cumulene carbon chain l-H2C5. A total of eleven rotational transitions, with Jup = 7-10 and Ka = 0 and 1, were detected in TMC-1 in the 31.0-50.4 GHz ...range using the Yebes 40m radio telescope. We derive a column density of (1.8±0.5)×1010 cm-2. In addition, we report observations of other cumulene carbenes detected previously in TMC-1, to compare their abundances with the newly detected cumulene carbene chain. We find that l-H2C5 is ~4.0 times less abundant than the larger cumulene carbene l-H2C6, while it is ~300 and ~500 times less abundant than the shorter chains l-H2C3 and l-H2C4. We discuss the most likely gas-phase chemical routes to these cumulenes in TMC-1 and stress that chemical kinetics studies able to distinguish between different isomers are needed to shed light on the chemistry of C n H2 isomers with n > 3.
Using the Yebes 40m and IRAM 30m radio telescopes, we detected a series of harmonically related lines with a rotational constant B 0=4460.590±0.001 MHz and a distortion constant D 0=0.511 ±0.005 kHz ...towards the cold dense core TMC-1. High-level-of-theory ab initio calculations indicate that the best possible candidate is protonated tricarbon monoxide, HC3O+. We have succeeded in producing this species in the laboratory and observed its J u -J l = 2-1 and 3-2 rotational transitions. Hence, we report the discovery of HC3O+ in space based on our observations, theoretical calculations, and laboratory experiments. We derive an abundance ratio N(C3O)/N(HC3O+)~7. The high abundance of the protonated form of C3O is due to the high proton affinity of the neutral species. The chemistry of O-bearing species is modelled, and predictions are compared to the derived abundances from our data for the most prominent O-bearing species in TMC-1.
We present the first astronomical detection of a diatomic negative ion, the cyanide anion CN-, and quantum mechanical calculations of the excitation of this anion by means of collisions with para-H2. ...The anion CN- is identified by observing the J = 2–1 and J = 3–2 rotational transitions in the C-star envelope IRC +10216 with the IRAM 30-m telescope. The U-shaped line profiles indicate that CN-, like the large anion C6H-, is formed in the outer regions of the envelope. Chemical and excitation model calculations suggest that this species forms from the reaction of large carbon anions with N atoms, rather than from the radiative attachment of an electron to CN, as is the case for large molecular anions. The unexpectedly high abundance derived for CN-, 0.25% relative to CN, indicates that its detection in other astronomical sources is likely. A parallel search for the small anion C2H- remains inconclusive, despite the previous tentative identification of the J = 1–0 rotational transition. The abundance of C2H- in IRC +10216 is found to be vanishingly small, <0.0014% relative to C2H.
Formamide (NH2CHO) has been proposed as a pre-biotic precursor with a key role in the emergence of life on Earth. While this molecule has been observed in space, most of its detections correspond to ...high-mass star-forming regions. Motivated by this lack of investigation in the low-mass regime, we searched for formamide, as well as isocyanic acid (HNCO), in 10 low- and intermediate-mass pre-stellar and protostellar objects. The present work is part of the IRAM Large Programme ASAI (Astrochemical Surveys At IRAM), which makes use of unbiased broad-band spectral surveys at millimetre wavelengths. We detected HNCO in all the sources and NH2CHO in five of them. We derived their abundances and analysed them together with those reported in the literature for high-mass sources. For those sources with formamide detection, we found a tight and almost linear correlation between HNCO and NH2CHO abundances, with their ratio being roughly constant – between 3 and 10 – across 6 orders of magnitude in luminosity. This suggests the two species are chemically related. The sources without formamide detection, which are also the coldest and devoid of hot corinos, fall well off the correlation, displaying a much larger amount of HNCO relative to NH2CHO. Our results suggest that, while HNCO can be formed in the gas-phase during the cold stages of star formation, NH2CHO forms most efficiently on the mantles of dust grains at these temperatures, where it remains frozen until the temperature rises enough to sublimate the icy grain mantles. We propose hydrogenation of HNCO as a likely formation route leading to NH2CHO.
We carried out an observational search for the recently discovered molecule H2NC, and its more stable isomer H2CN, toward eight cold dense clouds (L1544, L134N, TMC-2, Lupus-1A, L1489, TMC-1 NH3, ...L1498, and L1641N) and two diffuse clouds (B0415+379 and B0355+508) in an attempt to constrain its abundance in different types of interstellar regions and shed light on its formation mechanism. We detected H2NC in all but one of the cold dense clouds targeted, while H2CN was only detected in five out of the eight clouds. The column densities derived for both H2NC and H2CN are in the range 1011–1012 cm−2, and the abundance ratio H2NC/H2CN varies between 0.51 and >2.7. The metastable isomer H2NC is therefore widespread in cold dense clouds, where it is present with an abundance similar to that of H2CN. We did not detect H2NC or H2CN in any of the two diffuse clouds targeted, meaning we can make no conclusions regarding how the chemistry of H2NC and H2CN varies between dense and diffuse clouds. We find that the column density of H2NC is correlated with that of NH3, which strongly suggests that these two molecules are chemically linked, ammonia most likely being a precursor of H2NC through the C + NH3 reaction. We performed electronic structure and statistical calculations that show that both H2CN and H2NC can be formed in the C + NH3 reaction through two different channels involving two different transition states that are very close in energy. The predicted product branching ratio H2NC/H2CN is very method dependent, but values between 0.5 and 0.8 are the most likely. Therefore, both the astronomical observations and the theoretical calculations support the reaction C + NH3 being the main source of H2NC in interstellar clouds.
Calcium dicarbide, CaC2, has been characterized at high resolution in the laboratory, and its main isotopologue, 40CaC2, has been assigned to 14 rotational emission lines between 14 and 115 GHz, ...including 12 previously unassigned lines, in the expanding molecular envelope of the evolved carbon star IRC+10216. Aided by high-level quantum calculations and measurements of multiple isotopologues, CaC2 is determined to be a T-shaped molecule with a highly ionic bond linking the metal atom to the C2 unit, very similar in structure to isovalent magnesium dicarbide (MgC2). The excitation of CaC2 is characterized by a very low rotational temperature of 5.8 ± 0.6 K and a kinetic temperature of 36 ± 16 K, similar to values derived for MgC2. On the assumption that the emission originates from a 30″ shell in IRC+10216, the column density of CaC2 is (5.6 ± 1.7) × 1011 cm−2. CaC2 is only the second Ca-bearing molecule besides CaNC and only the second metal dicarbide besides MgC2 identified in space. Owing to the similarity between the predicted ion–molecule chemistry of Ca and Mg, a comparison of the CaC2 abundance with that of MgC2 and related species permits empirical inferences about the radiative association–dissociative recombination processes postulated to yield metal-bearing molecules in IRC+10216 and similar objects.
Circumstellar environments of oxygen-rich stars are among the strongest SiO maser emitters. Physical processes such as collisions, infrared pumping and overlaps favors the inversion of level ...population and produce maser emission at different vibrational states. Despite numerous observational and theoretical efforts, we still do not have an unified picture including all the physical processes involved in the SiO maser emission. The aim of this work is to provide homogeneous data in a large sample of oxygen-rich stars. We present a survey of 67 oxygen-rich stars from 7 to 1 mm, in their rotational transitions from
= 1 → 0 to
= 5 → 4, for vibrational numbers
from 0 to 6 in the three main SiO isotopologues. We have used one of the 34 m NASA antennas at Robledo and the IRAM 30 m radio telescope. The first tentative detection of a
= 6 line is reported, as well as the detection of new maser lines. The highest vibrational levels seem confined to small volumes, presumably close to the stars. The
= 1 → 0,
= 2 line flux is greater than the corresponding
= 1 in almost half of the sample, which may confirm a predicted dependence on the pulsation cycle. This database is potentially useful in models which should consider most of the physical agents, time dependency, and mass-loss rates. As by-product, we report detections of 27 thermal rotational lines from other molecules, including isotopologues of SiS, H
S, SO, SO
, and NaCl.
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-1 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 H 3 + with H2CCO.
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