Search

We report the first laboratory and interstellar detection of the alpha-cyano vinyl radical (H2CCCN). This species was produced in the laboratory by an electric discharge of a gas mixture of vinyl cyanide, CH2CHCN, and Ne, and its rotational spectrum was characterized using a Balle-Flygare narrowband-type Fourier-transform microwave spectrometer operating in the frequency region of 8-40 GHz. The observed spectrum shows a complex structure due to tunneling splittings between two torsional sublevels of the ground vibronic state, 0+ and 0-, derived from a large-amplitude inversion motion. In addition, the presence of two equivalent hydrogen nuclei makes necessary to discern between ortho- and para-H2CCCN. A least squares analysis reproduces the observed transition frequencies with a standard deviation of ca. 3 kHz. Using the laboratory predictions, this radical is detected in the cold dark cloud TMC-1 using the Yebes 40m telescope and the QUIJOTE line survey. The 404-303 and 505-404 rotational transitions, composed of several hyperfine components, were observed in the 31.0-50.4 GHz range. Adopting a rotational temperature of 6K we derive a column density of (1.4+/-0.2)e11 cm-2 and (1.1+/-0.2)e11 cm-2 for ortho-H2CCCN and para-H2CCCN, respectively. The reactions C + CH3CN, and perhaps also N + CH2CCH, emerge as the most likely routes to H2CCCN in TMC-1.

We report on the discovery of the C7N- anion towards the starless core TMC-1 and towards the carbon-rich evolved star IRC+10216. We used the data of the QUIJOTE line survey towards TMC-1 and found six lines in perfect harmonic frequency relation from J=27-26 up to J=32-31. The frequency of the lines can be reproduced with a rotational constant and a distortion constant of B=582.68490+/-0.00024 MHz and D=4.01+/-0.13 Hz, respectively. The standard deviation of the fit is 4 kHz. Towards IRC+10216, we identify 17 lines from J=27-26 up to J=43-42; their frequencies are also in harmonic relation, providing B=582.6827+/-0.00085 MHz and D=3.31+/-0.31 Hz. The nearly exact coincidence of the rotational and distortion constants in both sources points unambiguously to a common molecular carrier. Taking into account the chemical peculiarities of both sources, the carrier could be a radical or an anion. The radical can be discarded, as the observed lines belong to a singlet species. Hence, the most plausible carrier is an anion. High-level ab initio calculations indicate that C7N-, for which we compute a rotational constant of B=582.0 MHz and a dipole moment of 7.5 D, is the carrier of the lines in both sources. We predict the neutral C7N to have a ground electronic state 2Pi and a dipole moment around 1 D. Because of this low dipole moment value and to its much larger rotational partition function, its lines are expected to be well below the sensitivity of our data for both sources.

We found four series of harmonically related lines in IRC\,+10216 with the Yebes\,40m and IRAM\,30m telescopes. The first series corresponds to a molecule with a rotational constant, $B$, of 1448.5994$\pm$0.0013 MHz and a distortion constant, $D$, of 63.45$\pm$1.15 Hz and covers upper quantum numbers from $J_u$=11 up to 33 (B1449). The second series is fitted with $B$=1446.9380$\pm$0.0098 MHz and $D$=91$\pm$23 Hz and covers upper quantum numbers from $J_u$=11 up to 17 (B1447). The third series is fitted with $B$=598.7495$\pm$0.0011 MHz and D=6.13$\pm$0.43 Hz and covers quantum numbers from $J_u$=26 up to 41 (B599). Finally, the frequencies of the last series of lines can be reproduced with $B$=594.3176$\pm$0.0026 MHz and $D$=4.92$\pm$1.16 Hz (B594). The large values of $D$ point toward four metal-bearing carriers. After exploring all plausible candidates containing Na, Al, Mg, and other metals, our ab initio calculations indicate that the cations MgC$_4$H$^+$, MgC$_3$N$^+$, MgC$_6$H$^+$, and MgC$_5$N$^+$ must be the carriers of B1449, B1447, B599, and B594, respectively. These cations could be formed by the radiative association of Mg$^+$ with C$_4$H, C$_3$N, C$_6$H, and C$_5$N, respectively. We calculated the radiative association rate coefficient of Mg$^+$ with C$_4$H, C$_3$N, C$_6$H, and C$_5$N and incorporated them in our chemical model. The results confirm that the Mg-bearing cations can be formed through these radiative association reactions in the outer layers of IRC\,+10216. This is the first time that cationic metal-bearing species have been found in space. These results provide a new paradigm on the reactivity of ionized metals with abundant radicals and open the door for further characterization of similar species in metal-rich astrophysical environments.

We report the detection of methyl ketene towards TMC-1 with the QUIJOTE line survey. Nineteen rotational transitions with rotational quantum numbers ranging from J = 3 up to J = 5 and Ka =< 2 were identified in the frequency range 32.0-50.4 GHz, 11 of which arise above the 3{\sigma} level. We derived a column density for CH3CHCO of N=1.5x10^11 cm-2 and a rotational temperature of 9 K. Hence, the abundance ratio between ketene and methyl ketene, CH2CO/CH3CHCO, is 93. This species is the second C3H4O isomer detected. The other, trans-propenal (CH2CHCHO), corresponds to the most stable isomer and has a column density of N=(2.2+-0.3)x10^11 cm-2, which results in an abundance ratio CH2CHCHO/CH3CHCO of 1.5. The next non-detected isomer with the lowest energy is cis-propenal, which is therefore a good candidate for future discovery. We have carried out an in-depth study of the possible gas-phase chemical reactions involving methyl ketene to explain the abundance detected, achieving good agreement between chemical models and observations.

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 most of the cold dense clouds targeted, 7 out of 8, while H2CN was only detected in 5 out of 8 clouds. The column densities derived for both H2NC and H2CN are in the range 1e11-1e12 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 either H2NC or H2CN in any of the two diffuse clouds targeted, which does not allow to shed light on how the chemistry of H2NC and H2CN varies between dense and diffuse clouds. We found that the column density of H2NC is correlated with that of NH3, which strongly suggests that these two molecules are chemically linked, most likely ammonia being a precursor of H2NC through the C + NH3 reaction. We performed electronic structure and statistical calculations which show that both H2CN and H2NC can be formed in the C + NH3 reaction through two different channels involving two different transition states which lie 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 ones. Therefore, both the astronomical observations and the theoretical calculations support that the reaction C + NH3 is the main source of H2NC in interstellar clouds.

We present the detection of ethanol (C2H5OH), acetone (CH3COCH3), and propanal (C2H5CHO) toward the cyanopolyyne peak of TMC-1. These three O-bearing complex organic molecules are known to be present in warm interstellar clouds, but had never been observed in a starless core. The addition of these three new pieces to the puzzle of complex organic molecules in cold interstellar clouds stresses the rich chemical diversity of cold dense cores in stages prior to the onset of star formation. The detections of ethanol, acetone, and propanal were made in the framework of QUIJOTE, a deep line survey of TMC-1 in the Q band that is being carried out with the Yebes 40m telescope. We derive column densities of (1.1 +/- 0.3)e12 cm-2 for C2H5OH, (1.4 +/- 0.6)e11 cm-2 for CH3COCH3, and (1.9 +/- 0.7)e11 cm-2 for C2H5CHO. The formation of these three O-bearing complex organic molecules is investigated with the aid of a detailed chemical model which includes gas and ice chemistry. The calculated abundances at a time around 2e5 yr are in reasonable agreement with the values derived from the observations. The formation mechanisms of these molecules in our chemical model are as follows. Ethanol is formed on grains by addition of atomic carbon on methanol followed by hydrogenation and non-thermal desorption. Acetone and propanal are produced by the gas-phase reaction between atomic oxygen and two different isomers of the C3H7 radical, where the latter follows from the hydrogenation of C3 on grains followed by non-thermal desorption. A gas-phase route involving the formation of (CH3)2COH+ through several ion-neutral reactions followed by its dissociative recombination with electrons do also contribute to the formation of acetone.

The interstellar discovery of the five cyano derivatives of propene brings interest in analogous molecules that could be detected in similar astronomical environments. In this context, ethynyl-propene derivatives are good candidates to be observed in the Taurus Molecular Cloud (TMC-1), where other cyano and ethynyl derivatives of hydrocarbons such as ethane, allene, propene, and cyclopentadiene, among others, have been detected. We have investigated the pure rotational spectra of the five ethynyl-propene derivatives to enable their interstellar detections. These molecular species have been produced by an electric discharge and their rotational spectra were characterized using a Balle-Flygare narrow band-type Fourier-transform microwave spectrometer operating in the frequency region of 4-40 GHz. The spectral analysis allowed us to derive accurate spectroscopic parameters to obtain reliable frequency predictions for astronomical searches. We do not detect any of these species in TMC-1 but we derive upper limits for the abundances for the five isomers.

Pure rotational transitions of methacrolein oxide (MACRO) were observed by Fourier-transform microwave spectroscopy. Among the four low-lying conformers existing within an energy window of 3 kcal/mol, only the lowest-energy conformer, the anti-trans conformer, was detected in a discharged jet of a 1,3-diiode-2-methylprop-1-ene and O2 mixture diluted in Ar. Nineteen pure rotational transitions, in the frequency range from 10 to 25 GHz, most of them showing A/E splitting due to the methyl-top internal rotation, were observed and analyzed by the XIAM program, yielding the internal rotation barrier of 559 cm-1, which very well agrees with a theoretically calculated value, 558 cm-1, at the CCSD(T)/cc-pVTZ level of theory.

Aims. We investigate the outcome of an electrical discharge of naphthalene and search for the resulting products in the Taurus Molecular Cloud (TMC-1). Methods. Using chirped pulse Fourier transform microwave spectroscopy paired with an electric discharge source, we investigated products resulting from the naphthalene discharge. Quantum chemical calculations were used to help assign species and investigate potential reaction pathways relevant to the interstellar medium. These products were searched for in TMC-1 using the QUIJOTE line survey, covering 31.0-50.3 GHz. Results. We confirm the detection of ethynylbenzene in TMC-1, and we also present a new molecular species, 1,2-diethynylbenzene, which could play an important role in the formation of naphthalene. Over ten products have been identified as resulting from the discharge, with only one of these species found in a previous IR-UV discharge study of naphthalene. Conclusions. Ethynylbenzene has definitively been detected in TMC-1, and while we have identified a potentially important species for the formation of naphthalene and an exothermic reaction pathway, there is no current indication of its presence in TMC-1.

Continuing Q-band (31- 50 GHz) integrations on IRC +10216 with the Yebes 40 m telescope have now reached sub-millikelvin noise with hundreds of new lines arising above an average 3 detection limit of 0.71 mK (as low as 0.45 mK in the lower frequency end). The recent discovery of the C7Nanion and the relatively large abundance of the HC9N member of the cyanopolyyne family opens the door for searching in the data for harmonically related series of lines belonging to singlet species, with intensities close to the detection limit, that could belong to heavier anions. One such series has been found with rotational quantum numbers from J = 52 51 up to J = 74 73, with at least 15 distinguishable features clearly detected as isolated or partly blended. There are two main candidates for the carriers of the series: C9Nand/or C10H, for which our high-level-of-theory ab initio calculations predict a quite compatible rotational constant of ~300 MHz. In this paper we discuss, based on our ab initio calculations and also on chemical models, which of these two candidates is the most likely carrier. There is more evidence for the C10Hcandidate. It would be, to date, the heaviest anion discovered in space through a series of detected individual lines.

We report on the detection of a series of six lines in the ultra-deep Q-band integration toward IRC+10216 carried out with the Yebes 40m telescope, which are in harmonic relation with integer quantum numbers J from 12 to 18. After a detailed analysis of all possible carriers, guided by high-level quantum chemical calculations, we conclude that the lines belong to HMgCCCN, named hydromagnesium cyanoacetylide. The rotational temperature and column density derived for HMgCCCN are 17.1 +/- 2.8K and (3.0 +/- 0.6) e12 cm-2, respectively. The observed abundance ratio between MgCCCN and HMgCCCN is 3. In addition, we report the discovery in space, also toward IRC+10216, of sodium cyanoacetylide, NaCCCN, for which accurate laboratory data are available. For this species we derive a rotational temperature of 13.5 +/- 1.7K and a column density of (1.2 +/- 0.2) e11 cm-2.

The recent interstellar detection of cyanonaphthalenes bring interest in related aromatic molecular species that could be present in similar astronomical environments. In this context, ethynyl derivatives of naphthalene are promising candidates to be observed in the Taurus Molecular Cloud (TMC-1), where cyanonaphthalenes together with cyano- and ethynyl- derivatives of cyclopentadiene and benzene have been detected. To enable the interstellar searches for ethynyl derivatives of naphthalene, their pure rotational spectra need to be investigated in the laboratory. We have observed for the first time the rotational spectra of 1- and 2-ethynylnaphthalene species using a broadband Fourier-transform microwave spectrometer operating in the 2-8 GHz frequency region. Accurate spectroscopic parameters are derived from the analysis of the experimental spectra, allowing for reliable predictions for astronomical searches. Our searches in TMC-1 for both isomers provide upper limits for the abundances of these species.

We report on the discovery of two new molecules, HCCCHCCC and HCCCCS, towards the starless core TMC-1 in the Taurus region from the QUIJOTE line survey in the 31.1-50.2 GHz frequency range. We identify a total of twenty-nine lines of HCCCHCCC and six rotational transitions of HCCCCS. The rotational quantum numbers range from Ju=10 up to 15 and Ka <=2 for HCCCHCCC and Ju=21/2 up to 31/2 for HCCCCS. We derived a column density for HCCCHCCC of N=(1.3+/-0.2)x10^11 cm-2 with a rotational temperature of 6+/-1 K, while for HCCCCS we derived N=(9.5+/-0.8)x10^10 cm-2 and Trot =10+/-1 K. The abundance of HCCCHCCC is higher than that of its recently discovered isomer, l-H2C6. If we compare HCCCCS with its related molecules, HCS and HCCS, we obtain abundance ratios HCS/HCCCCS=58 and HCCS/HCCCCS=7.2. We investigated the formation of these two molecules using chemical modelling calculations. The observed abundances can be accounted for by assuming standard gas-phase formation routes involving neutral-neutral reactions and ion-neutral reactions.

We report the detection of magnesium dicarbide, MgC2, in the laboratory at centimeter wavelengths and assign 24MgC225MgC2, and 26MgC2 to 14 unidentified lines in the radio spectrum of the circumstellar envelope of the evolved carbon star IRC+10216. The structure of MgC2 is found to be T-shaped with a highly ionic bond between the metal atom and the C2 unit, analogous to other dicarbides containing electropositive elements. A two-temperature excitation model of the MgC2 emission lines observed in IRC+10216 yields a very low rotational temperature of 6 ± 1 K, a kinetic temperature of 22 ± 13 K, and a column density of (1.0 ± 0.3) × 1012 cm−2. The abundance of MgC2 relative to the magnesium-carbon chains MgCCH, MgC4H, and MgC6H is 1:2:22:20 and provides a new constraint on the sequential radiative association-dissociative recombination mechanisms implicated in the production of metal-bearing molecules in circumstellar environments.

The previous detection of two species related to the non polar molecule cyanogen (NCCN), its protonated form (NCCNH+) and one metastable isomer (CNCN), in cold dense clouds supported the hypothesis that dicyanopolyynes are abundant in space. Here we report the first identification in space of NC4NH+, which is the protonated form of NC4N, the second member of the series of dicyanopolyynes after NCCN. The detection was based on the observation of six harmonically related lines within the Yebes 40m line survey of TMC-1 QUIJOTE. The six lines can be fitted to a rotational constant B = 1293.90840 +/- 0.00060 MHz and a centrifugal distortion constant D = 28.59 +/- 1.21 Hz. We confidently assign this series of lines to NC4NH+ based on high-level ab initio calculations, which supports the previous identification of HC5NH+ by Marcelino et al. (2020) from the observation of a series of lines with a rotational constant 2 MHz lower than that derived here. The column density of NC4NH+ in TMC-1 is (1.1 +1.4 -0.6)e10 cm-2, which implies that NC4NH+ is eight times less abundant than NCCNH+. The species CNCN, previously reported toward L483 and tentatively in TMC-1, is confirmed in this latter source. We estimate that NCCN and NC4N are present in TMC-1 with abundances a few times to one order of magnitude lower than HC3N and HC5N, respectively. This means that dicyanopolyynes NC-(CC)n-CN are present at a lower level than the corresponding monocyanopolyynes HCC-(CC)n-CN. The reactions of the radicals CN and C3N with HNC arise as the most likely formation pathways to NCCN and NC4N in cold dense clouds.

Fourier transform microwave spectra for two isomers of the chlorine substituted vinyl radical have been observed in the 4-52 GHz frequency region. The observed radicals (2A') have been generated using electric discharges of diluted dichloro derivatives of ethylene as molecular precursors. Fine and hyperfine components observed for each rotational transition are fully assigned in the present study to two isotopologues (35Cl and 37Cl), and precise molecular constants are determined for both radicals.