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The gas-phase abundance of carbon, x_C = C/H, and its depletion factors are essential parameters for understanding the gas and solid compositions that are ultimately incorporated into planets. The majority of protoplanetary disks are born in clusters and, as a result, are exposed to external FUV radiation. These FUV photons potentially affect the disk's evolution, chemical composition, and line excitation. We present the first detection of the [CI]609um fine-structure line of neutral carbon (CI), achieved with ALMA, toward one of these disks, d203-506, in the Orion Nebula Cluster. We also report the detection of CI forbidden and permitted lines (from electronically excited states up to 10 eV) observed with JWST in the IR. These lines trace the irradiated outer disk and photo-evaporative wind. Contrary to the common belief that these IR lines are C+ recombination lines, we find that they are dominated by FUV-pumping of CI followed by fluorescence cascades. They trace the transition from atomic to molecular gas, and their intensities scale with G0. The lack of outstanding IR OI fluorescent emission, however, implies a sharper attenuation of external FUV radiation with E > 12 eV (~Lyman-beta). This is related to a lower effective FUV dust absorption cross section compared to that of interstellar grains, implying a more prominent role for FUV shielding by the CI photoionization continuum. The [CI]609um intensity is proportional to N(CI) and can be used to infer x_C. We derive x_C ~ 1.4E-4. This implies that there is no major depletion of volatile carbon compared to x_C measured in the natal cloud, hinting at a young disk. We also show that external FUV radiation impacts the outer disk and wind by vertically shifting the water freeze-out depth, which results in less efficient grain growth and settling. This shift leads to nearly solar gas-phase C/O abundance ratios in these irradiated layers., Comment: Accepted for publication in A&A Letters. 14 pages including Appendices

Cross sections and rate coefficients for the Dissociative Recombination (DR) of the NS+ ion induced by collisions with low-energy electrons are reported for temperatures between 10 and 1000 K, relevant to a large range of interstellar cloud temperatures. Uncertainties are discussed for these rates. Comparisons are made with DR rates for the isovalent NO+ molecular ion which are found to be much faster. The present findings lead to a moderate dissociative reaction rate coefficient, smaller by a factor of 2 than the current estimates reported in the different kinetic databases for a temperature of 10 K. We consider that our rate coefficients obtained through multichannel quantum defect theory for NS+ are likely to be better than those displayed in the different kinetic databases., Comment: 6 pages, 8 figures, 2 tables

We report the first detection in space of a complete sample of nine doubly substituted isotopologues of HCCCN towards the cyanopolyyne peak of TMC-1 using observations of the QUIJOTE line survey taken with the Yebes 40 m telescope. We detected D13CCCN, DC13CCN, DCC13CN, DCCC15N, H13C13CCN, H13CC13CN, HC13C13CN, HCC13C15N, and HC13CC15N through their J=4-3 and J=5-4 lines in the 7 mm window. In addition, we present an extensive analysis of the emission of HCCCN and its singly substituted isotopologues through a large velocity gradient model of the lines detected at 7 mm and 3 mm using the Yebes 40 m and the IRAM 30 m telescopes, respectively. The derived column densities for all the isotopologues are consistent in the two spectral bands for an H2 volume density of 1e4 cm-3 and a kinetic temperature of 10 K. Whereas we observed a 13C fractionation for HCC13CN and other double isotopologues with a 13C atom adjacent to the nitrogen atom, we derived similar C/13C abundance ratios for the three 13C substituted species of DCCCN. This suggests additional chemical discrimination for deuterated isotopologues of HCCCN. Finally, we present the spatial distribution of the J=4-3 and J=5-4 lines from the singly substituted species observed with the Yebes 40 m telescope. The emission peak of the spatial distribution of DCCCN appears to be displaced by 40'' with respect to that of HCCCN and the 13C and 15N isotopologues. In addition to a different formation route for the deuterated species, we could also expect that this differentiation owing to the deuterium fractionation is more efficient at low temperatures, and therefore, that deuterated species trace a colder region of the cloud., Comment: Accepted for publication in A&A

To understand the chemistry of sulphur (S) in the interstellar medium, models need to be tested by observations of S-bearing molecules in different physical conditions. We analyse observations obtained with the IRAM 30m telescope towards 15 well-known cores classified in the three main evolutionary stages of the high-mass star-formation process: high-mass starless cores,high-mass protostellar objects, and ultracompact HII regions. We detected rotational lines of SO, SO+, NS, C34S, 13CS, SO2, CCS, H2S, HCS+, OCS, H2CS, and CCCS. We also analyse for the first time lines of the NO molecule to complement the analysis. From a local thermodynamic equilibrium approach, we have derived column densities of each species and excitation temperatures. Based on a statistical analysis on the line widths and the excitation temperatures, we find that: NS, C34S, 13CS, CCS, and HCS+ trace cold, quiescent, and likely extended material; OCS, and SO2 trace warmer, more turbulent, and likely denser and more compact material; SO and perhaps SO+ trace both quiescent and turbulent material depending on the target. The abundances of SO, SO2, and H2S show the strongest positive correlations with the kinetic temperature, believed to be an evolutionary indicator. Moreover, the sum of all molecular abundances show an enhancement of gaseous S from the less evolved to the more evolved stages. These trends could be due to the increasing amount of S sputtered from dust grains owing to the increasing protostellar activity with evolution. The average abundances in each evolutionary group increase especially in the oxygen-bearing molecules, perhaps due to the increasing abundance of atomic oxygen with evolution owing to photodissociation of water in gas phase. Our observational work represents a test-bed for theoretical studies aimed at modelling the chemistry of sulphur during the evolution of high-mass star-forming cores, Comment: 16 pages. 3 appendices. Accepted for publication in A&A

We present 5 deg^2 (~250 pc^2) HCN, HNC, HCO+, and CO J=1-0 maps of the Orion B GMC, complemented with existing wide-field [CI] 492 GHz maps, as well as new pointed observations of rotationally excited HCN, HNC, H13CN, and HN13C lines. We detect anomalous HCN J=1-0 hyperfine structure line emission almost everywhere in the cloud. About 70% of the total HCN J=1-0 luminosity arises from gas at A_V < 8 mag. The HCN/CO J=1-0 line intensity ratio shows a bimodal behavior with an inflection point at A_V < 3 mag typical of translucent gas and UV-illuminated cloud edges. We find that most of the HCN J=1-0 emission arises from extended gas with n(H2) ~< 10^4 cm^-3, even lower density gas if the ionization fraction is > 10^-5 and electron excitation dominates. This result explains the low-A_V branch of the HCN/CO J=1-0 intensity ratio distribution. Indeed, the highest HCN/CO ratios (~0.1) at A_V < 3 mag correspond to regions of high [CI] 492 GHz/CO J=1-0 intensity ratios (>1) characteristic of low-density PDRs. Enhanced FUV radiation favors the formation and excitation of HCN on large scales, not only in dense star-forming clumps. The low surface brightness HCN and HCO+ J=1-0 emission scale with I_FIR (a proxy of the stellar FUV radiation field) in a similar way. Together with CO J=1-0, these lines respond to increasing I_FIR up to G0~20. On the other hand, the bright HCN J=1-0 emission from dense gas in star-forming clumps weakly responds to I_FIR once the FUV radiation field becomes too intense (G0>1500). The different power law scalings (produced by different chemistries, densities, and line excitation regimes) in a single but spatially resolved GMC resemble the variety of Kennicutt-Schmidt law indexes found in galaxy averages. As a corollary for extragalactic studies, we conclude that high HCN/CO J=1-0 line intensity ratios do not always imply the presence of dense gas., Comment: accepted for publication in A&A. 24 pages, 18 figures, plus Appendix. Abridged Abstract

We present a new gas-grain chemical model for the combined isotopic fractionation of carbon and nitrogen in molecular clouds, in which the isotope chemistry of carbon and nitrogen is coupled with a time-dependent description of spin-state chemistry. We updated the rate coefficients of some isotopic exchange reactions considered in the literature, and present here a set of new exchange reactions involving molecules substituted in $\rm ^{13}C$ and $\rm ^{15}N$ simultaneously. We apply the model to a series of zero-dimensional simulations representing a set of physical conditions across a prototypical prestellar core, exploring the deviations of the isotopic abundance ratios in the various molecules from the elemental isotopic ratios as a function of physical conditions and time. We find that the $\rm ^{12}C/^{13}C$ ratio can deviate from the elemental ratio by up to a factor of several depending on the molecule, and that there are highly time-dependent variations in the ratios. The $\rm HCN/H^{13}CN$ ratio, for example, can obtain values of less than 10 depending on the simulation time. The $\rm ^{14}N/^{15}N$ ratios tend to remain close to the assumed elemental ratio within $\sim$ ten per cent, with no clear trends as a function of the physical conditions. Abundance ratios between $\rm ^{13}C$-containing molecules and $\rm ^{13}C$+$\rm ^{15}N$-containing molecules show somewhat increased levels of fractionation due to the newly included exchange reactions, though still remaining within a few tens of per cent of the elemental $\rm ^{14}N/^{15}N$ ratio. Our results imply the existence of gradients in isotopic abundance ratios across prestellar cores, suggesting that detailed simulations are required to interpret observations of isotopically substituted molecules correctly, especially given that the various isotopic forms of a given molecule do not necessarily trace the same gas layers., Comment: Accepted to A&A; abstract abridged to meet arXiv requirements

(Abridged) Massive stars can determine the evolution of molecular clouds with their strong ultraviolet (UV) radiation fields. Moreover, UV radiation is relevant in setting the thermal gas pressure in star-forming clouds, whose influence can extend from the rims of molecular clouds to entire star-forming galaxies. Probing the fundamental structure of nearby molecular clouds is therefore crucial to understand how massive stars shape their surrounding medium and how fast molecular clouds are destroyed, specifically at their UV-illuminated edges, where models predict an intermediate zone of neutral atomic gas between the molecular cloud and the surrounding ionized gas whose size is directly related to the exposed physical conditions. We present the highest angular resolution (~$0.5$", corresponding to $207$ au) and velocity-resolved images of the molecular gas emission in the Horsehead nebula, using CO J=3-2 and HCO$^+$ J=4-3 observations with ALMA. We find that CO and HCO$^+$ are present at the edge of the cloud, very close to the ionization (H$^+$/H) and dissociation fronts (H/H$_2$), suggesting a very thin layer of neutral atomic gas (<$650$ au) and a small amount of CO-dark gas ($A_V=0.006-0.26$ mag) for stellar UV illumination conditions typical of molecular clouds in the Milky Way. The new ALMA observations reveal a web of molecular gas filaments with an estimated thermal gas pressure of $P_{\mathrm{th}} = (2.3 - 4.0) \times 10^6$ K cm$^{-3}$, and the presence of a steep density gradient at the cloud edge that can be well explained by stationary isobaric PDR models with pressures consistent with our estimations. However, in the HII region and PDR interface, we find $P_{\mathrm{th,PDR}} > P_{\mathrm{th,HII}}$, suggesting the gas is slightly compressed. Therefore, dynamical effects cannot be completely ruled out and even higher angular observations will be needed to unveil their role., Comment: 15 pages, 1 table, 9 figures; Accepted for publication in A&A

HCN, HNC, and their isotopologues are ubiquitous molecules that can serve as chemical thermometers and evolutionary tracers to characterize star-forming regions. Despite their importance in carrying information that is vital to studies of the chemistry and evolution of star-forming regions, the collision rates of some of these molecules have not been available for rigorous studies in the past. We perform an up-to-date gas and dust chemical characterization of two different star-forming regions, TMC 1-C and NGC 1333-C7, using new collisional rates of HCN, HNC, and their isotopologues. We investigated the possible effects of the environment and stellar feedback in their chemistry and their evolution. With millimeter observations, we derived their column densities, the C and N isotopic fractions, the isomeric ratios, and the deuterium fractionation. The continuum data at 3 mm and 850 $\mu$m allowed us to compute the emissivity spectral index and look for grain growth as an evolutionary tracer. The H$^{13}$CN/HN$^{13}$C ratio is anticorrelated with the deuterium fraction of HCN, thus it can readily serve as a proxy for the temperature. The spectral index $(\beta\sim 1.34-2.09)$ shows a tentative anticorrelation with the H$^{13}$CN/HN$^{13}$C ratio, suggesting grain growth in the evolved, hotter, and less deuterated sources. Unlike TMC 1-C, the south-to-north gradient in dust temperature and spectral index observed in NGC 1333-C7 suggests feedback from the main NGC 1333 cloud. With this up-to-date characterization of two star-forming regions, we found that the chemistry and the physical properties are tightly related. The dust temperature, deuterium fraction, and the spectral index are complementary evolutionary tracers. The large-scale environmental factors may dominate the chemistry and evolution in clustered star-forming regions., Comment: 25 pages, 20 figures

We compute the radiative ro-vibrational emission spectrum of H2 involving quasibound states via a simple numerical method of resolution of the Schr\"odinger equation by introducing a modifed effective molecular potential. The comparison of the eigenvalues obtained with our approximation and other theoretical methods based on scattering resonance properties is excellent. Electric quadrupole and magnetic dipole contributions are calculated and we confirm the previous computations of Forrey of the electric quadrupole transition Einstein coeffcients. The astrophysical relevance of such quasibound levels is emphasized, Comment: 10 pages,1 figure, 4 tables. Molecular Physics

In the context of the IRAM 30m Large Program GEMS, we present a study of thioformaldehyde in several starless cores located in star-forming filaments of Taurus, Perseus, and Orion. We investigate the influence of the environmental conditions on the abundances of these molecules in the cores, and the effect of time evolution. We have modelled the observed lines of H2CS, HDCS, and D2CS using the radiative transfer code RADEX. We have also used the chemical code Nautilus to model the evolution of these species depending on the characteristics of the starless cores. We derive column densities and abundances for all the cores. We also derive deuterium fractionation ratios, Dfrac, to determine and compare the evolutionary stage between different parts of each star-forming region. Our results indicate that the north region of the B213 filament in Taurus is more evolved than the south, while the north-eastern part of Perseus presents an earlier evolutionary stage than the south-western zone. Model results also show that Dfrac decreases with the cosmic-ray ionisation rate, while it increases with density and with the degree of sulphur depletion. In particular, we only reproduce the observations when the initial sulphur abundance in the starless cores is at least one order of magnitude lower than the solar elemental sulphur abundance. The progressive increase in HDCS/H2CS and D2CS/H2CS with time makes these ratios powerful tools for deriving the chemical evolutionary stage of starless cores. However, they cannot be used to derive the temperature of these regions, since both ratios present a similar evolution at two different temperature ranges (7-11 K and 15-19 K). Regarding chemistry, (deuterated) thioformaldehyde is mainly formed through gas-phase reactions (double-replacement and neutral-neutral displacement reactions), while surface chemistry plays an important role as a destruction mechanism., Comment: 31 pages, 26 figures

Rate coefficients for dissociative recombination and state-to-state rotational transitions of the D$_{2}^{+}$ ion induced by collisions with very low-energy electrons have been reported following our previous studies on HD$^{+}$ and H$_{2}^{+}$ [9,10]. The same molecular structure data sets, excitations ($N_{i}^{+} \rightarrow$ $N_{f}^{+}=N_{i}^{+}+2$ for $N_{i}^{+}=0$ to $10$) and de-excitations ($N_{i}^{+}$ $\rightarrow$ $N_{f}^{+}=N_{i}^{+}-2$, for $N_{i}^{+}=2$ to $10$) were used for collision energies ranging from $0.01$ meV to $0.3$ eV. Isotopic effects for dissociative recombination and rotational transitions of the vibrationally relaxed targets are presented., Comment: 7 pages, 7 figures, 4 tables

We report the first detection in space of the single deuterated isotopologue of methyldiacetylene, CH2DC4H. A total of 12 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 allowed us to obtain, for the first time, the spectroscopic parameters of this deuterated isotopologue. We derived a column density of (5.5+/-0.2)e11 cm-2. The abundance ratio between CH3C4H and CH2DC4H is 24+/-2. This ratio is similar to that found for the CH3C3N/CH2DC3N analogue system, which is 22+/-2.We did not detect the deuterated species CH3C4D, which has already been observed in laboratory experiments. The detection of deuterated CH3C4H allows us to extend the discussion on the chemical mechanisms of deuterium fractionation at work in TMC-1 using a new gas-phase chemical model with multiply deuterated molecules. Introducing a possible deuterium exchange reaction between CH3CCH and atomic deuterium allows us to account for the CH3C4H/CH2DC4H abundance ratio., Comment: Accepted for publication in A&A Letters on December 20th. arXiv admin note: text overlap with arXiv:2106.03404

We report the first detection in space of the single deuterated isotopologue of methylcyanoacetylene, CH$_2$DC$_3$N. A total of fifteen rotational transitions, with $J$ = 8-12 and $K_a$ = 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 $(8.0\pm 0.4) \times 10^{10}$ cm$^{-2}$. The abundance ratio between CH$_3$C$_3$N and CH$_2$DC$_3$N is $\sim$22. We also theoretically computed the principal spectroscopic constants of $^{13}$C isotopologues of CH$_3$C$_3$N and CH$_3$C$_4$H and those of the deuterated isotopologues of CH$_3$C$_4$H for which we could expect a similar degree of deuteration enhancement. However, we have not detected either CH$_2$DC$_4$H nor CH$_3$C$_4$D nor any $^{13}$C 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 H$_2$D$^+$., Comment: Accepted for publication in A&A Letters

The large disparity in physical conditions from the diffuse interstellar medium (ISM) to denser clouds such as photon-dominated regions (PDRs) triggers an evolution of the dust properties (i.e. composition, size, and shape). The gas physics and chemistry are tightly connected to these dust properties and are therefore affected by dust evolution and especially the nano-grain depletion in the outer irradiated part of PDRs. We highlight the influence of nano-grain depletion on the gas physics and chemistry in the Horsehead nebula, a prototypical PDR. We used a model for atomic and molecular gas in PDRs, the Meudon PDR code, using diffuse ISM-like dust and Horsehead-like dust to study the influence of nano-grain depletion on the gas physics and chemistry, focusing on the impact on photoelectric heating and H2 formation and, therefore, on the H2 gas lines. We find that nano-grain depletion in the Horsehead strongly affects gas heating through the photoelectric effect and thus the gas temperature and the H2 formation, hence the H -> H2 position. Consequently, the first four pure rotational lines of H2 (e.g. 0-0 S(0), S(1), S(2), and S(3)) vary by a factor of 2 to 14. The 0-0 S(3) line that is often underestimated in models is underestimated even more when taking nano-grain depletion into account due to the decrease in gas heating through the photoelectric effect. This strongly suggests that our understanding of the excitation of H2 and/or of heating processes in the Horsehead, and more generally in PDRs, is still incomplete. Nano-grain depletion in the outer part of the Horsehead has a strong influence on several gas tracers that will be prominent in JWST observations of irradiated clouds. We therefore need to take this depletion into account in order to improve our understanding of the Horsehead, and more generally PDRs, and to contribute to the optimal scientific return of the mission., Comment: Accepted in A&A, comments welcome

We report the first detection in space of the two doubly deuterated isotopologues of methyl acetylene. The species CHD2CCH and CH2DCCD were identified in the dense core L483 through nine and eight, respectively, rotational lines in the 72-116 GHz range using the IRAM 30m telescope. The astronomical frequencies observed here were combined with laboratory frequencies from the literature measured in the 29-47 GHz range to derive more accurate spectroscopic parameters for the two isotopologues. We derive beam-averaged column densities of (2.7 +/- 0.5)e12 cm-2 for CHD2CCH and (2.2 +/- 0.4)e12 cm-2 for CH2DCCD, which translate to abundance ratios CH3CCH/CHD2CCH = 34 +/- 10 and CH3CCH/CH2DCCD = 42 +/- 13. The doubly deuterated isotopologues of methyl acetylene are only a few times less abundant than the singly deuterated ones, concretely around 2.4 times less abundant than CH3CCD. The abundances of the different deuterated isotopologues with respect to CH3CCH are reasonably accounted for by a gas-phase chemical model in which deuteration occurs from the precursor ions C3H6D+ and C3H5D+, when the ortho-to-para ratio of molecular hydrogen is sufficiently low. This points to gas-phase chemical reactions, rather than grain-surface processes, as responsible for the formation and deuterium fractionation of CH3CCH in L483. The abundance ratios CH2DCCH/CH3CCD = 3.0 +/- 0.9 and CHD2CCH/CH2DCCD = 1.25 +/- 0.37 observed in L483 are consistent with the statistically expected values of three and one, respectively, with the slight overabundance of CHD2CCH compared to CH2DCCD being well explained by the chemical model., Comment: Accepted for publication in A&A

Gas phase Elemental abundances in Molecular CloudS (GEMS) is an IRAM 30m Large Program designed to estimate the S, C, N, and O depletions and gas ionization degree, X(e-), in a set of star-forming filaments of Taurus, Perseus and Orion. Our immediate goal is to build up a complete database of molecular abundances that can serve as an observational basis for estimating X(e-) and the C, O, N, and S depletions through chemical modeling. We observed and derived the abundances of 14 species (13CO, C18O, HCO+, H13CO+, HC18O+, HCN, H13CN, HNC, HCS+, CS, SO, 34SO, H2S, and OCS) in 244 positions, covering the AV 3 to 100 mag, n(H2) a few 10$^{3}$ to 10$^6$ cm$^{-3}$, and Tk 10 to 30 K ranges in these clouds, avoiding protostars, HII regions, and outflows. A statistical analysis is carried out to identify general trends between different species and with physical parameters. Relations between molecules reveal strong linear correlations which define three different families: (1) 13CO and C18O; (2) H13CO+, HC18O+, H13CN, and HNC; and (3) the S-bearing molecules. The abundances of the CO isotopologs increase with the gas kinetic temperature until TK 15 K. For higher temperatures, the abundance remains constant with a scatter of a factor of 3. The abundances of H13CO+, HC18O+, H13CN, and HNC are well correlated with each other, and all of them decrease with molecular hydrogen density, following the law n(H2)$^{-0.8\pm0.2}$. The abundances of S-bearing species also decrease with n(H2) at a rate of (S-bearing/H)gas n(H2)$^{-0.6\pm0.1}$. The abundances of molecules belonging to groups 2 and 3 do not present any clear trend with gas temperature. At scales of molecular clouds, the C18O abundance is the quantity that better correlates with the cloud mass. We discuss the utility of the 13CO/C18O, HCO+/H13CO+, and H13CO+/H13CN abundance ratios as chemical diagnostics of star formation in external galaxies., Comment: 28 pages, 22 figures. Accepted for publication in A&A

CS is among the most abundant gas-phase S-bearing molecules in cold dark molecular clouds. It is easily observable with several transitions in the millimeter wavelength range, and has been widely used as a tracer of the gas density in the interstellar medium in our Galaxy and external galaxies. Chemical models fail to account for the observed CS abundances when assuming the cosmic value for the elemental abundance of sulfur. The CS+O -> CO + S reaction has been proposed as a relevant CS destruction mechanism at low temperatures, and could explain the discrepancy between models and observations. Its reaction rate has been experimentally measured at temperatures of 150-400 K, but the extrapolation to lower temperatures is doubtful. Here we calculate the CS+O reaction rate at temperatures <150 K which are prevailing in the interstellar medium. We performed ab initio calculations to obtain the three lowest PES of the CS+O system. These PESs are used to study the reaction dynamics, using several methods to eventually calculate the CS+O thermal reaction rates. We compare the results of our theoretical calculations for 150-400 K with those obtained in the laboratory. Our detailed theoretical study on the CS+O reaction, which is in agreement with the experimental data obtained at 150-400 K, demonstrates the reliability of our approach. After a careful analysis at lower temperatures, we find that the rate constant at 10 K is negligible, which is consistent with the extrapolation of experimental data using the Arrhenius expression. We use the updated chemical network to model the sulfur chemistry in TMC1 based on molecular abundances determined from GEMS project observations. In our model, we take into account the expected decrease of the cosmic ray ionization rate along the cloud. The abundance of CS is still overestimated when assuming the cosmic value for the sulfur abundance., Comment: 11 pages, 10 figures, accepted in Astronomy & Astrophysics

C-fractionation has been studied from a theoretical point of view with different models of time-dependent chemistry, including both isotope-selective photodissociation and low-temperature isotopic exchange reactions. Recent chemical models predict that the latter may lead to a depletion of $^{13}$C in nitrile-bearing species, with $^{12}$C/$^{13}$C ratios two times higher than the elemental abundance ratio of 68 in the local ISM. Since the carbon isotopic ratio is commonly used to evaluate the $^{14}$N/$^{15}$N ratios with the double-isotope method, it is important to study C-fractionation in detail to avoid incorrect assumptions. In this work we implemented a gas-grain chemical model with new isotopic exchange reactions and investigated their introduction in the context of dense and cold molecular gas. In particular, we investigated the $^{12}$C/$^{13}$C ratios of HNC, HCN, and CN using a grid of models, with temperatures and densities ranging from 10 to 50 K and 2$\times$10$^{3}$ to 2$\times$10$^{7}$ cm$^{-3}$, respectively. We suggest a possible $^{13}$C exchange through the $^{13}$C + C$_{3}$ $\rightarrow$ $^{12}$C +$^{13}$CC$_{2}$ reaction, which does not result in dilution, but rather in $^{13}$C enhancement, for molecules formed starting from atomic carbon. This effect is efficient in a range of time between the formation of CO and its freeze-out on grains. Furthermore, we show that the $^{12}$C/$^{13}$C ratios of nitriles are predicted to be a factor 0.8-1.9 different from the local value of 68 for massive star-forming regions. This result also affects the $^{14}$N/$^{15}$N ratio: a value of 330 obtained with the double-isotope method is predicted to be 260-1150, depending on the physical conditions. Finally, we studied the $^{12}$C/$^{13}$C ratios by varying the cosmic-ray ionization rate: the ratios increase with it because of secondary photons and cosmic-ray reactions., Comment: The published exponent in the A&A journal of the second rate coefficient of Table 1 is a misprint

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. Our goal is to investigate the H$_{2}$S chemistry in dark clouds, as this stable molecule is a potential sulphur reservoir. Using millimeter observations of CS, SO, H$_{2}$S, and their isotopologues, we determine the physical conditions and H$_{2}$S abundances along the cores TMC 1-C, TMC 1-CP, and Barnard 1b. The gas-grain model Nautilus is then used to model the sulphur chemistry and explore the impact of photo-desorption and chemical desorption on the H$_2$S abundance. Our model shows that chemical desorption is the main source of gas-phase H$_2$S in dark cores. The measured H$_{2}$S abundance can only be fitted if we assume that the chemical desorption rate decreases by more than a factor of 10 when $n_{\rm H}>2\times10^{4}$. This change in the desorption rate is consistent with the formation of thick H$_2$O and CO ice mantles on grain surfaces. The observed SO and H$_2$S 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. We conclude that the gaseous H$_2$S abundance is well reproduced, assuming undepleted sulphur abundance and chemical desorption as the main source of H$_2$S. The behavior of the observed H$_{2}$S abundance suggests a changing desorption efficiency, which would probe the snowline in these cores. Our model, however, overestimates the observed gas-phase CS abundance. Given the uncertainty in the sulphur chemistry, our data are consistent with a cosmic elemental S abundance with an uncertainty of a factor of 10., Comment: 23 pages, 16 figures

Deuterium and lithium are light elements of high cosmological and astrophysical importance. In this work we report the first detection of deuterated molecules and a search for lithium hydride, 7LiH, at redshift z=0.89 in the spiral galaxy intercepting the line of sight to the quasar PKS1830-211. We used ALMA to observe several submillimeter lines of ND, NH2D, and HDO, and their related isotopomers NH2, NH3, and H2^18O, in absorption against the southwest image of the quasar, allowing us to derive XD/XH abundance ratios. The absorption spectra mainly consist of two distinct narrow velocity components for which we find remarkable differences. One velocity component shows XD/XH abundances that is about 10 times larger than the primordial elemental D/H ratio, and no variability of the absorption profile during the time span of our observations. [...] The second component has XD/XH abundances that are 100 times larger than the primordial D/H ratio, a deepening of the absorption by a factor of two within a few months, and a rich chemical composition, with relative enhancements of N2H+, CH3OH, SO2, and complex organic molecules. We therefore speculate that this component is associated with the analog of a Galactic dark cloud, while the first component is likely more diffuse. Our search for the 7LiH (1--0) line was unsuccessful and we derive an upper limit 7LiH/H2 = 4 x 10^-13 (3sigma) in the z=0.89 absorber toward PKS1830-211. Besides, with ALMA archival data, we could not confirm the previous tentative detections of this line in the z=0.68 absorber toward B0218+357; we derive an upper limit 7LiH/H2 = 5 x 10^-11 (3sigma), although this is less constraining than our limit toward PKS1830-211. We conclude that, as in the Milky Way, only a tiny fraction of lithium nuclei are possibly bound in LiH in these absorbers at intermediate redshift., Comment: Accepted for publication in A&A

The high spectral resolution R about 45,000 provided by IGRINS (Immersion Grating INfrared Spectrometer) at MacDonald Observatory and R 100,000 achieved by CRIRES (CRyogenic high-resolution InfraRed Echelle Spectrograph) at VLT (Very Large Telescope) challenges the present knowledge of infrared spectra. aims We aim to predict the full infrared spectrum of molecular hydrogen at a comparable accuracy. methods We take advantage of the recent theoretical ab initio studies on molecular hydrogen to compute both the electric quadrupole and magnetic dipole transitions taking place within the ground electronic molecular state of hydrogen. results We computed the full infrared spectrum of molecular hydrogen at an unprecedented accuracy and derive for the first time the emission probabilities including both electric quadrupole ($\Delta J = 0, \pm$2) and magnetic dipole transitions ($\Delta J = 0$) as well as the total radiative lifetime of each rovibrational state. Inclusion of magnetic dipole transitions increases the emission probabilities by factors of a few for highly excited rotational levels, which occur in the 3-20 $\mu$ range}, Comment: 6 pages, 1 figure, 2 tables. Full Table 2 is only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/cat/J/A+A/630/A58. It can also be obtained on request to evelyne.roueff@obspm.fr

(abridged) The far-UV wavelength range (912-2000A) provides access to atomic and molecular transitions of many species the interstellar medium (ISM), circumgalactic medium (CGM), and intergalactic medium, within phases spanning a wide range of ionization, density, temperature, and molecular gas fraction. Far-UV space telescopes have enabled detailed studies of the ISM in the Milky Way thanks to absorption features appearing in the UV spectra of hot stars and yielding fundamental insights into the composition and physical characteristics of all phases of the ISM along with the processes that influence them. However, we have yet to design a spectrometer able to observe the full UV domain at resolving power R>10^5 with a signal-to-noise ratio SNR>500. Such a resolution is necessary to resolve lines from both the cold molecular hydrogen and the warm metal ions with a turbulent velocity of about 1 km s-1, and to differentiate distinct velocity components. Future UV spectroscopic studies of the Milky Way ISM must revolutionize our understanding of the ISM as a dynamical, unstable, and magnetized medium, and rise to the challenge brought forward by current theories. Another interesting prospect is to transpose the same level of details that has been reached for the Milky Way to the ISM in external galaxies, in particular in metal-poor galaxies, where the ISM chemical composition, physical conditions, and topology change dramatically, with significant consequences on the star-formation properties. Finally, we need to be able to perform statistical analyses of background quasar lines of sight intersecting the CGM of galaxies at various redshifts and to comprehend the role of gas exchanges and flows for galaxy evolution., Comment: This ESA white paper draws from and expands on the following white papers previously submitted for the Astro 2020 Decadal Survey, Gry et al. (2019), Lebouteiller et al. (2019), and Yan et al. (2019). The original ESA white paper was reformatted as a 2-column paper for the present document. (arXiv admin note: substantial text overlap with arXiv:1903.07295, arXiv:1903.06250, arXiv:1903.11065)

We use observations of chlorine-bearing species in molecular absorbers at intermediate redshifts to investigate chemical properties and $^{35}$Cl/$^{37}$Cl isotopic ratios in the absorbing sightlines. Chloronium (H$_2$Cl$^+$) is detected along three independent lines of sight in the z=0.89 and z=0.68 molecular absorbers located in front of the lensed quasars PKS 1830-211 and B 0218+357, respectively. Hydrogen chloride (HCl) was observed only toward PKS 1830-211, and is found to behave differently from H$_2$Cl$^+$. It is detected in one line of sight with an abundance ratio [H$_2$Cl$^+$]/[HCl] $\sim 1$, but remains undetected in the other, more diffuse, line of sight, with a ratio [H$_2$Cl$^+$]/[HCl]~$>17$. The absorption profiles of these two chlorine-bearing species are compared to other species and discussed in terms of the physical properties of the absorbing gas. Our findings are consistent with the picture emerging from chemical models where different species trace gas with different molecular hydrogen fraction. The $^{35}$Cl/$^{37}$Cl isotopic ratios are measured in the different lines of sight and are discussed in terms of stellar nucleosynthesis., Comment: Accepted for publication in Astronomy & Astrophysics 10 pages, 2 figures

A very low ortho-to-para ratio (OPR) of 0.1-0.5 was previously reported in the Orion Bar photon-dominated region (PDR), based on observations of two optically thin $\mathrm{H_2^{18}O}$ lines which were analyzed by using a single-slab large velocity gradient model. The corresponding spin temperature does not coincide with the kinetic temperature of the molecular gas in this UV-illuminated region. This was interpreted as an indication of water molecules being formed on cold icy grains which were subsequently released by UV photodesorption. A more complete set of water observations in the Orion Bar, including seven $\mathrm{H_2^{16}O}$ lines and one $\mathrm{H_2^{18}O}$ line, carried out using Herschel/HIFI instrument, was reanalyzed using the Meudon PDR code to derive gas-phase water abundance and the OPR, taking into account the steep density and temperature gradients present in the region. The model line intensities are in good agreement with the observations assuming that water molecules formed with an OPR corresponding to thermal equilibrium conditions at the local kinetic temperature of the gas and when solely considering gas-phase chemistry and water gas-grain exchanges through adsorption and desorption. Gas-phase water is predicted to arise from a region deep into the cloud, corresponding to a visual extinction of $A_{\mathrm{V}} \sim 9$, with a $\mathrm{H_2^{16}O}$ fractional abundance of $\sim 2\times 10^{-7}$ and column density of $(1.4 \pm 0.8) \times 10^{15}$ cm$^{-2}$ for a total cloud depth of $A_{\mathrm{V}}=15$. A line-of-sight average ortho-to-para ratio of $2.8 \pm 0.2$ is derived. The observational data are consistent with a nuclear spin isomer repartition corresponding to the thermal equilibrium at a temperature of $36 \pm 2$ K, much higher than the spin temperature previously reported for this region and close to the gas kinetic temperature in the water-emitting gas.

Aims. Our goal is to complete the inventory of S-bearing molecules and their abundances in the prototypical photodissociation region (PDR) the Horsehead nebula to gain insight into sulphur chemistry in UV irradiated regions. Based on the WHISPER millimeter (mm) line survey, our goal is to provide an improved and more accurate description of sulphur species and their abundances towards the core and PDR positions in the Horsehead. Methods. The Monte Carlo Markov chain (MCMC) methodology and the molecular excitation and radiative transfer code RADEX were used to explore the parameter space and determine physical conditions and beam-averaged molecular abundances. Results. A total of 13 S-bearing species (CS, SO, SO2, OCS, H2CS - both ortho and para - HDCS, C2S, HCS+, SO+, H2S, S2H, NS and NS+) have been detected in the two targeted positions. This is the first detection of SO+ in the Horsehead and the first detection of NS+ in any PDR. We find a differentiated chemical behaviour between C-S and O-S bearing species within the nebula. The C-S bearing species C2S and o-H2CS present fractional abundances a factor grater than two higher in the core than in the PDR. In contrast, the O-S bearing molecules SO, SO2, and OCS present similar abundances towards both positions. A few molecules, SO+, NS, and NS+, are more abundant towards the PDR than towards the core, and could be considered as PDR tracers. Conclusions. This is the first complete study of S-bearing species towards a PDR. Our study shows that CS, SO, and H2S are the most abundant S-bearing molecules in the PDR with abundances of a few 1E-9. We recall that SH, SH+, S, and S+ are not observable at the wavelengths covered by the WHISPER survey. At the spatial scale of our observations, the total abundance of S atoms locked in the detected species is < 1E-8, only ~0.1% of the cosmic sulphur abundance., Comment: 15 pages, 7 figures, 6 tables

We present an IRAM 30m line survey of the dense core L483 in the 3 mm band. We detected 71 molecules (140 including different isotopologs), most of which are present in the cold and quiescent ambient cloud. Of particular interest among the detected molecules are the cis isomer of HCOOH, the complex organic molecules HCOOCH3, CH3OCH3, and C2H5OH, a wide variety of carbon chains, nitrogen oxides like N2O, and saturated molecules like CH3SH. In general, fractional molecular abundances in L483 are systematically lower than in TMC-1 (especially for carbon chains), tend to be higher than in L1544 and B1-b, and are similar to those in L1527. Apart from the overabundance of carbon chains in TMC-1, we find that L483 does not have a marked chemical differentiation with respect to starless/prestellar cores like TMC-1 and L1544, although it does chemically differentiate from Class 0 hot corino sources like IRAS 16293-2422. This fact suggests that the chemical composition of the ambient cloud of some Class 0 sources could be largely inherited from the dark cloud starless/prestellar phase. We also derived isotopic ratios for a variety of molecules, some of which show isotopic anomalies like an extreme depletion in 13C for one of the two isotopologs of c-C3H2, a drastic enrichment in 18O for SO and HNCO (SO being also largely enriched in 17O), and different abundances for the two 13C substituted species of C2H and the two 15N substituted species of N2H+. We report the first detection in space of some minor isotopologs like c-C3D. The exhaustive chemical characterization of L483 presented here, together with similar studies of other prestellar and protostellar sources, should allow us to identify the main factors that regulate the chemical composition of cores along the process of formation of low-mass protostars., Comment: Published in A&A. Abstract abridged. Changes with respect to previous version: english edited and updated information on deuterated molecules in IRAS 16293-2422

Absorption lines of H$_2$ and HD molecules observed at high redshift in the line of sight towards quasars are a test ground to search for variation of the proton-to-electron mass ratio $\mu$. For this purpose, results from astronomical observations are compared with a compilation of molecular data of the highest accuracy, obtained in laboratory studies as well as in first-principles calculations. Aims: A comprehensive line list is compiled for H$_2$ and HD absorption lines in the Lyman ($B^1\Sigma_u^+$ - $X^1\Sigma_g^+$) and Werner ($C^1\Pi_u$ - $X^1\Sigma_g^+$) band systems up to the Lyman cutoff at 912 Angstroms. Molecular parameters listed for each line $i$ are the transition wavelength $\lambda_i$, the line oscillator strength $f_i$, the radiative damping parameter of the excited state $\Gamma_i$, and the sensitivity coefficient $K_i$ for a variation of the proton-to-electron mass ratio. Methods: The transition wavelengths $\lambda_i$ for the H$_2$ and HD molecules are determined by a variety of advanced high-precision spectroscopic experiments involving narrowband vacuum ultraviolet lasers, Fourier-transform spectrometers, and synchrotron radiation sources. Results for the line oscillator strengths $f_i$, damping parameters $\Gamma_i$, and sensitivity coefficients $K_i$ are obtained in theoretical quantum chemical calculations. Results: A new list of molecular data is compiled for future analyses of cold clouds of hydrogen absorbers, specifically for studies of $\mu$-variation from quasar data. The list is applied in a refit of quasar absorption spectra of B0642$-$5038 and J1237$+$0647 yielding constraints on a variation of the proton-to-electron mass ratio $\Delta\mu/\mu$ consistent with previous analyses., Comment: 4 pages. Accepted by Astronomy and Astrophysics. The 3 tables containing the molecular data are available at http://vizier.u-strasbg.fr/viz-bin/VizieR?-source=J/A+A/622/A127 and are contained in the source package of the arXiv submission (in "Other formats")

The transition between atomic and molecular hydrogen is associated with important changes in the structure of interstellar clouds, and marks the beginning of interstellar chemistry. Because of the relatively simple networks controlling their abundances, molecular ions are usually good probes of the underlying physical conditions including for instance the fraction of gas in molecular form or the fractional ionization. In this paper we focus on three possible probes of the molecular hydrogen column density, HCO+, HOC+, and CF+. We presented high sensitivity ALMA absorption data toward a sample of compact HII regions and bright QSOs with prominent foreground absorption, in the ground state transitions of the molecular ions HCO+, HOC+, and CF+ and the neutral species HCN and HNC, and from the excited state transitions of C3H+(4-3) and 13CS(2-1). These data are compared with Herschel absorption spectra of the ground state transition of HF and p-H2O. We show that the HCO+, HOC+, and CF+ column densities are well correlated with each other. HCO+ and HOC+ are tightly correlated with p-H2O, while they exhibit a different correlation pattern with HF depending on whether the absorbing matter is located in the Galactic disk or in the central molecular zone. We report new detections of C3H+ confirming that this ion is ubiquitous in the diffuse matter, with an abundance relative to H2 of ~7E-11. We confirm that the CF+ abundance is lower than predicted by simple chemical models and propose that the rate of the main formation reaction is lower by a factor of about 3 than usually assumed. In the absence of CH or HF data, we recommend to use the ground state transitions of HCO+, CCH, and HOC+ to trace diffuse molecular hydrogen, with mean abundances relative to H2 of 3E-9, 4E-8 and 4E-11., Comment: 15 pages, 9 Figures, accepted by Astronomy and Astrophysics. slightly modified abstract

The Barnard 1b core shows signatures of being at the earliest stages of low-mass star formation, with two extremely young and deeply embedded protostellar objects. Hence, this core is an ideal target to study the structure and chemistry of the first objects formed in the collapse of prestellar cores. We present ALMA Band 6 spectral line observations at ~0.6'' of angular resolution towards Barnard 1b. We have extracted the spectra towards both protostars, and used a Local Thermodynamic Equilibrium (LTE) model to reproduce the observed line profiles. B1b-S shows rich and complex spectra, with emission from high energy transitions of complex molecules, such as CH3OCOH and CH3CHO, including vibrational level transitions. We have tentatively detected for the first time in this source emission from NH2CN, NH2CHO, CH3CH2OH, CH2OHCHO, CH3CH2OCOH and both aGg' and gGg' conformers of (CH2OH)2. This is the first detection of ethyl formate (CH3CH2OCOH) towards a low-mass star forming region. On the other hand, the spectra of the FHSC candidate B1b-N are free of COMs emission. In order to fit the observed line profiles in B1b-S, we used a source model with two components: an inner hot and compact component (200 K, 0.35'') and an outer and colder one (60 K, 0.6''). The resulting COM abundances in B1b-S range from 1e-13 for NH2CN and NH2CHO, up to 1e-9 for CH3OCOH. Our ALMA Band 6 observations reveal the presence of a compact and hot component in B1b-S, with moderate abundances of complex organics. These results indicate that a hot corino is being formed in this very young Class 0 source., Comment: Accepted for publication in A&A

GEMS is an IRAM 30m Large Program whose aim is determining the elemental depletions and the ionization fraction in a set of prototypical star-forming regions. This paper presents the first results from the prototypical dark cloud TMC 1. Extensive millimeter observations have been carried out with the IRAM 30m telescope (3mm and 2mm) and the 40m Yebes telescope (1.3cm and 7mm) to determine the fractional abundances of CO, HCO+, HCN, CS, SO, HCS+, and N2H+ in three cuts which intersect the dense filament at the well-known positions TMC 1-CP, TMC 1-NH3, and TMC 1-C, covering a visual extinction range from Av~3 to ~20mag. Two phases with differentiated chemistry can be distinguished: i) the translucent envelope with molecular hydrogen densities of (1-5)x10$^3$ cm$^{-3}$; and ii) the dense phase, located at Av>10mag, with molecular hydrogen densities >10$^4$ cm$^{-3}$. Observations and modeling show that the gas phase abundances of C and O progressively decrease along the C+/C/CO transition zone where C/H~8x10$^{-5}$ and C/O~0.8-1, until the beginning of the dense phase at Av~10 mag. This is consistent with the grain temperatures being below the CO evaporation temperature in this region. In the case of sulfur, a strong depletion should occur before the translucent phase where we estimate a S/H~(0.4 - 2.2) x10$^{-6}$, an abundance ~7-40 times lower than the solar value. A second strong depletion must be present during the formation of the thick icy mantles to achieve the values of S/H measured in the dense cold cores (S/H~8x10$^{-8}$). Based on our chemical modeling, we constrain the value of $\zeta_{\rm H_2}$ to ~(0.5 - 1.8) x10$^{-16}$ s$^{-1}$ in the translucent cloud., Comment: 26 pages, 20 figures, A&A in press

Cross sections are presented for dissociative recombination and electron-impact vibrational excitation of the ArH+ molecular ion at electron energies appropriate for the interstellar environment. The R-matrix method is employed to determine the molecular structure data, i.e. the position and width of the resonance states. The cross sections and the corresponding Maxwellian rate coefficients are computed using a method based on the Multichannel Quantum Defect Theory. The main result of the paper is the very low dissociative recombination rate found at temperatures below 1000K. This is in agreement with the previous upper limit measurement in merged beams and offers a realistic explanation to the presence of ArH+ in exotic interstellar conditions., Comment: 6 pages; 7 figures

The isocyanate radical (NCO) is the simplest molecule containing the backbone of the peptide bond, C(=O)-N. This bond has a prebiotic interest since is the one linking two amino acids to form large chains of proteins. It is also present in some organic molecules observed in space such as HNCO, NH2CHO and CH3NCO. In this letter we report the first detection in space of NCO towards the dense core L483. We also report the identification of the ion H2NCO+, definitively confirming its presence in space, and observations of HNCO, HOCN, and HCNO in the same source. For NCO, we derive a column density of 2.2e12 cm-2, which means that it is only about 5 times less abundant than HNCO. We find that H2NCO+, HOCN and HCNO have abundances relative to HNCO of 1/400, 1/80, and 1/160, respectively. Both NCO and H2NCO+ are involved in the production of HNCO and several of its isomers. We have updated our previous chemical models involving NCO and the production of the CHNO isomers. Taking into account the uncertainties in the model, the observed abundances are reproduced relatively well. Indeed, the detection of NCO and H2NCO+ in L483 supports the chemical pathways to the formation of the detected CHNO isomers. Sensitive observations of NCO in sources where other molecules containing the C(=O)-N subunit have been detected could help in elucidating its role in prebiotic chemistry in space., Comment: Accepted for publication in A&A Letters

Evidence is mounting that the small bodies of our Solar System, such as comets and asteroids, have at least partially inherited their chemical composition from the first phases of the Solar System formation. It then appears that the molecular complexity of these small bodies is most likely related to the earliest stages of star formation. It is therefore important to characterize and to understand how the chemical evolution changes with solar-type protostellar evolution. We present here the Large Program "Astrochemical Surveys At IRAM" (ASAI). Its goal is to carry out unbiased millimeter line surveys between 80 and 272 GHz of a sample of ten template sources, which fully cover the first stages of the formation process of solar-type stars, from prestellar cores to the late protostellar phase. In this article, we present an overview of the surveys and results obtained from the analysis of the 3 mm band observations. The number of detected main isotopic species barely varies with the evolutionary stage and is found to be very similar to that of massive star-forming regions. The molecular content in O- and C- bearing species allows us to define two chemical classes of envelopes, whose composition is dominated by either a) a rich content in O-rich complex organic molecules, associated with hot corino sources, or b) a rich content in hydrocarbons, typical of Warm Carbon Chain Chemistry sources. Overall, a high chemical richness is found to be present already in the initial phases of solar-type star formation., Comment: 19 pages, 7 figures, 5 Tables

We report the detection in space of a new molecular species which has been characterized spectroscopically and fully identified from astrophysical data. The observations were carried out with the 30m IRAM telescope. The molecule is ubiquitous as its $J$=2$\rightarrow$1 transition has been found in cold molecular clouds, prestellar cores, and shocks. However, it is not found in the hot cores of Orion-KL and in the carbon-rich evolved star IRC+10216. Three rotational transitions in perfect harmonic relation J'=2/3/5 have been identified in the prestellar core B1b. The molecule has a 1Sigma electronic ground state and its J=2-1 transition presents the hyperfine structure characteristic of a molecule containing a nucleus with spin 1. A careful analysis of possible carriers shows that the best candidate is NS+. The derived rotational constant agrees within 0.3-0.7 % with ab initio calculations. NS+ was also produced in the laboratory to unambiguously validate the astrophysical assignment. The observed rotational frequencies and determined molecular constants confirm the discovery of the nitrogen sulfide cation in space. The chemistry of NS+ and related nitrogen-bearing species has been analyzed by means of a time-dependent gas phase model. The model reproduces well the observed NS/NS+ abundance ratio, in the range 30-50, and indicates that NS+ is formed by reactions of the neutral atoms N and S with the cations SH+ and NH+, respectively., Comment: Accepted for publication in ApJ Letters

The formation epoch of protostellar disks is debated because of the competing roles of rotation, turbulence, and magnetic fields in the early stages of low-mass star formation. Magnetohydrodynamics simulations of collapsing cores predict that rotationally supported disks may form in strongly magnetized cores through ambipolar diffusion or misalignment between the rotation axis and the magnetic field orientation. Detailed studies of individual sources are needed to cross check the theoretical predictions. We present 0.06-0.1" resolution images at 350 GHz toward B1b-N and B1b-S, which are young class 0 protostars, possibly first hydrostatic cores. The images have been obtained with ALMA, and we compare these data with magnetohydrodynamics simulations of a collapsing turbulent and magnetized core. The submillimeter continuum emission is spatially resolved by ALMA. Compact structures with optically thick 350 GHz emission are detected toward both B1b-N and B1b-S, with 0.2 and 0.35" radii (46 and 80 au at the Perseus distance of 230 pc), within a more extended envelope. The flux ratio between the compact structure and the envelope is lower in B1b-N than in B1b-S, in agreement with its earlier evolutionary status. The size and orientation of the compact structure are consistent with 0.2" resolution 32 GHz observations obtained with the Very Large Array as a part of the VANDAM survey, suggesting that grains have grown through coagulation. The morphology, temperature, and densities of the compact structures are consistent with those of disks formed in numerical simulations of collapsing cores. Moreover, the properties of B1b-N are consistent with those of a very young protostar, possibly a first hydrostatic core. These observations provide support for the early formation of disks around low-mass protostars., Comment: 8 pages, 10 PDF figures. Accepted for publication in A&A. Uses aa and natbib latex macros

The z=0.89 molecular absorber toward PKS1830-211 provides us with the opportunity to probe the chemical and physical properties of the interstellar medium in the disk of a galaxy at a look-back time of half the present age of the Universe. Recent ALMA observations of hydrides have unveiled the multi-phase composition of this source's interstellar medium along two absorbing sightlines. Here, we report ALMA observations of CH+ and SH+, and of their 13C- and 34S- isotopologues, as potential tracers of energetic processes in the interstellar medium. CH+ and 13CH+ are detected toward both images of PKS1830-211, CH+ showing the deepest and broadest absorption among all species observed so far. The [CH+]/[13CH+] abundance ratio is ~100 in the south-west line of sight. [...] Toward the north-east image, we find an even larger value of [CH+]/[13CH+], 146 +/- 43, although with a large uncertainty. This sightline intercepts the absorber at a larger galactocentric radius than the southwestern one, where material might be less processed in stellar nucleosynthesis. In contrast to CH+ and its 13C isotopologue, SH+ and 34SH+ are only detected on the south-west sightline. These are the first detections of extragalactic SH+ and interstellar 34SH+. The spectroscopic parameters of SH+ are reevaluated and improved rest frequencies of 34SH+ are obtained. The [CH+]/[SH+] column density ratios show a large difference between the two lines of sight: ~25 and >600 toward the SW and NE image, respectively. We are not able to shed light on the formation process of CH+ and SH+ with these data, but the differences in the two sightlines toward PKS1830-211 suggest that their absorptions arise from gas with molecular fraction gtrsim 10%, with SH+ tracing significantly higher molecular fractions than CH+., Comment: accepted for publication in A&A

Observations towards L1630 in the Orion B molecular cloud, comprising the iconic Horsehead Nebula, allow us to study the interplay between stellar radiation and a molecular cloud under relatively benign conditions, that is, intermediate densities and an intermediate UV radiation field. Contrary to the well-studied Orion Molecular Cloud 1 (OMC1), which hosts much harsher conditions, L1630 has little star formation. We aim to relate the [CII] fine-structure line emission to the physical conditions predominant in L1630 and compare it to studies of OMC1. The [CII] $158\,\mu\mathrm{m}$ emission from an area of $12' \times 17'$ in L1630 was observed using the upGREAT instrument onboard SOFIA. Of the [CII] emission from the mapped area 95%, $13\,L_{\odot}$, originates from the molecular cloud; the adjacent HII region contributes only 5%, that is, $1\,L_{\odot}$. From comparison with other data (CO (1-0)-line emission, far-infrared (FIR) continuum studies, emission from polycyclic aromatic hydrocarbons (PAHs)), we infer a gas density of the molecular cloud of $n_{\mathrm{H}}\sim 3\cdot 10^3\,\mathrm{cm^{-3}}$, with surface layers, including the Horsehead Nebula, having a density of up to $n_{\mathrm{H}}\sim 4\cdot 10^4\,\mathrm{cm^{-3}}$. The temperature of the surface gas is $T\sim 100\,\mathrm{K}$. The average [CII] cooling efficiency within the molecular cloud is $1.3\cdot 10^{-2}$. The fraction of the mass of the molecular cloud within the studied area that is traced by [CII] is only $8\%$. Our PDR models are able to reproduce the FIR-[CII] correlations and also the CO (1-0)-[CII] correlations. Finally, we compare our results on the heating efficiency of the gas with theoretical studies of photoelectric heating by PAHs, clusters of PAHs, and very small grains, and find the heating efficiency to be lower than theoretically predicted, a continuation of the trend set by other observations., Comment: 23 pages, 30 figures, accepted for publication in Astronomy & Astrophysics

Recent detections of complex organic molecules in dark clouds have rekindled interest in the astrochemical modeling of these environments. Because of its relative closeness and rich molecular complexity, TMC-1 has been extensively observed to study the chemical processes taking place in dark clouds. We use local thermodynamical equilibrium radiative transfer modeling coupled with a Bayesian statistical method which takes into account outliers to analyze the data from the Nobeyama spectral survey of TMC-1 between 8 and 50 GHz. We compute the abundance relative to molecular hydrogen of 57 molecules, including 19 isotopologues in TMC-1 along with their associated uncertainty. The new results are in general agreement with previous abundance determination from Ohishi & Kaifu and the values reported in the review from Agundez & Wakelam. However, in some cases, large opacity and low signal to noise effects allow only upper or lower limits to be derived, respectively., Comment: Accepted for publication in ApJS

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 mm, H2 S(3) rotational line at 9.3 mm, 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 1.9x10^(-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., Comment: The main text has 4 pages, 2 pages of Appendix, 4 figures, 1 table. Accepted for publication in Astronomy and Astrophysics letters

Barnard B1b has revealed as one of the most interesting globules from the chemical and dynamical point of view. It presents a rich molecular chemistry characterized by large abundances of deuterated and complex molecules. Furthermore, it hosts an extremely young Class 0 object and one candidate to First Hydrostatic Core (FHSC). Our aim was to determine the cosmic ray ionization rate and the depletion factors in this extremely young star forming region. We carried out a spectral survey towards Barnard 1b as part of the IRAM Large program ASAI using the IRAM 30-m telescope at Pico Veleta (Spain). This provided a very complete inventory of neutral and ionic C-, N- and S- bearing species with, up to our knowledge, the first secure detections of the deuterated ions DCS+ and DOCO+. We used a state-of-the-art pseudo-time-dependent gas-phase chemical model to determine the value of the cosmic ray ionization rate and the depletion factors. The observational data were well fitted with $\zeta_{H_2}$ between 3E-17 s$^{-1}$ and 1E-16 s$^{-1}$. Elemental depletions were estimated to be ~10 for C and O, ~1 for N and ~25 for S. Barnard B1b presents similar depletions of C and O than those measured in pre-stellar cores. The depletion of sulfur is higher than that of C and O but not as extreme as in cold cores. In fact, it is similar to the values found in some bipolar outflows, hot cores and photon-dominated regions. Several scenarios are discussed to account for these peculiar abundances. We propose that it is the consequence of the initial conditions (important outflows and enhanced UV fields in the surroundings) and a rapid collapse (~0.1 Myr) that permits to maintain most S- and N-bearing species in gas phase to great optical depths. The interaction of the compact outflow associated with B1b-S with the surrounding material could enhance the abundances of S-bearing molecules, as well., Comment: Paper accepted in Astronomy and Astrophysics; 28 pags, 21 figures

We present Herschel, ALMA Compact Array (ACA), and Caltech Submillimeter Observatory (CSO) observations of the prestellar core in L1689N, which has been suggested to be interacting with a molecular outflow driven by the nearby solar type protostar IRAS 16293-2422. This source is characterized by some of the highest deuteration levels seen in the interstellar medium. The change in the NH2D line velocity and width across the core provides clear evidence of an interaction with the outflow, traced by the high-velocity water emission. Quiescent, cold gas, characterized by narrow line widths is seen in the NE part of the core, while broader, more disturbed line profiles are seen in the W/SW part. Strong N2D+ and ND3 emission is detected with the ACA, extending S/SW from the peak of the single-dish NH2D emission. The ACA data also reveal the presence a compact dust continuum source, with a mean size of ~1100 au, a central density of (1-2) 10^7 cm-3, and a mass of 0.2-0.4 Msun. The dust emission peak is displaced ~5" to the south with respect to the N2D+ and ND3 emission, as well as the single-dish dust continuum peak, suggesting that the northern, quiescent part of the core is characterized by spatially extended continuum emission, which is resolved out by the interferometer. We see no clear evidence of fragmentation in this quiescent part of the core, which could lead to a second generation of star formation, although a weak dust continuum source is detected in this region in the ACA data., Comment: Accepted for publication in the Astrophysical Journal, 20 pages, 10 figures, 2 tables

Understanding the processes that could lead to enrichment of molecules in $^{15}$N atoms is of particular interest in order to shed light on the relatively large variations observed in the $^{14}$N/$^{15}$N ratio in various solar system environments. Currently, the sample of molecular clouds where $^{14}$N/$^{15}$N ratios have been measured is small and has to be enlarged in order to allow statistically significant studies. In particular, the N$_2$H$^+$ molecule currently shows the largest spread of $^{14}$N/$^{15}$N ratios in high-mass star forming regions. However, the $^{14}$N/$^{15}$N ratio in N$_2$H$^+$ was obtained in only two low-mass star forming regions (L1544 and B1b). The current work extends this sample to a third dark cloud. We targeted the 16293E prestellar core, where the N$^{15}$NH$^+$ $J$=1-0 line was detected. Using a model previously developed for the physical structure of the source, we solved the molecular excitation with a non-local radiative transfer code. For that purpose, we computed specific collisional rate coefficients for the N$^{15}$NH$^+$-H$_2$ collisional system. As a first step of the analysis, the N$_2$H$^+$ abundance profile was constrained by reproducing the N$_2$H$^+$ $J$=1-0 and 3-2 maps. A scaling factor was then applied to this profile to match the N$^{15}$NH$^+$ $J$=1-0 spectrum. We derive a column density ratio N$_2$H$^+$ / N$^{15}$NH$^+$ = $330^{+170}_{-100}$. The current estimate $\sim$330 agrees with the value typical of the elemental isotopic ratio in the local ISM. It is however lower than in some other cores, where values as high as 1300 have been reported.

More complete knowledge of galaxy evolution requires understanding the process of star formation and interaction between the interstellar radiation field and the interstellar medium in galactic environments traversing a wide range of physical parameter space. Here we focus on the impact of massive star formation on the surrounding low metallicity ISM in 30 Doradus in the Large Magellanic Cloud. A low metal abundance, as is the case of some galaxies of the early universe, results in less ultra-violet shielding for the formation of the molecular gas necessary for star formation to proceed. The half-solar metallicity gas in this region is strongly irradiated by the super star cluster R136, making it an ideal laboratory to study the structure of the ISM in an extreme environment. Our spatially resolved study investigates the gas heating and cooling mechanisms, particularly in the photo-dissociation regions where the chemistry and thermal balance are regulated by far-ultraviolet photons (6 eV< h\nu <13.6 eV). We present Herschel observations of far-infrared fine-structure lines obtained with PACS and SPIRE/FTS. We have combined atomic fine-structure lines from Herschel and Spitzer observations with ground-based CO data to provide diagnostics on the properties and the structure of the gas by modeling it with the Meudon PDR code. We derive the spatial distribution of the radiation field, the pressure, the size, and the filling factor of the photodissociated gas and molecular clouds. We find a range of pressure of ~ 10^5 - 1.7x10^6 cm^{-3} K and a range of incident radiation field G_UV ~ 10^2 - 2.5x10^4 through PDR modeling. Assuming a plane-parallel geometry and a uniform medium, we find a total extinction of 1-3 mag , which correspond to a PDR cloud size of 0.2 to 3pc, with small CO depth scale of 0.06 to 0.5pc. We also determine the three dimensional structure of the gas. (Abridged), Comment: 20 pages, 23 figures, accepted in A&A

The availability of collisional rate coefficients is a prerequisite for an accurate interpretation of astrophysical observations, since the observed media often harbour densities where molecules are populated under non--LTE conditions. In the current study, we present calculations of rate coefficients suitable to describe the various spin isomers of multiply deuterated ammonia, namely the ND$_2$H and ND$_3$ isotopologues. These calculations are based on the most accurate NH$_3$--H$_2$ potential energy surface available, which has been modified to describe the geometrical changes induced by the nuclear substitutions. The dynamical calculations are performed within the close--coupling formalism and are carried out in order to provide rate coefficients up to a temperature of $T$ = 50K. For the various isotopologues/symmetries, we provide rate coefficients for the energy levels below $\sim$ 100 cm$^{-1}$. Subsequently, these new rate coefficients are used in astrophysical models aimed at reproducing the NH$_2$D, ND$_2$H and ND$_3$ observations previously reported towards the prestellar cores B1b and 16293E. We thus update the estimates of the corresponding column densities and find a reasonable agreement with the previous models. In particular, the ortho--to--para ratios of NH$_2$D and NHD$_2$ are found to be consistent with the statistical ratios.

The 1$_{11}$-1$_{01}$ lines of ortho and para--NH$_2$D (o/p-NH$_2$D), respectively at 86 and 110 GHz, are commonly observed to provide constraints on the deuterium fractionation in the interstellar medium. In cold regions, the hyperfine structure due to the nitrogen ($^{14}$N) nucleus is resolved. To date, this splitting is the only one which is taken into account in the NH$_2$D column density estimates. We investigate how the inclusion of the hyperfine splitting caused by the deuterium (D) nucleus affects the analysis of the rotational lines of NH$_2$D. We present 30m IRAM observations of the above mentioned lines, as well as APEX o/p-NH$_2$D observations of the 1$_{01}$-0$_{00}$ lines at 333 GHz. The hyperfine spectra are first analyzed with a line list that only includes the hyperfine splitting due to the $^{14}$N nucleus. We find inconsistencies between the line widths of the 1$_{01}$-0$_{00}$ and 1$_{11}$-1$_{01}$ lines, the latter being larger by a factor of $\sim$1.6$\pm0.3$. Such a large difference is unexpected given the two sets of lines are likely to originate from the same region. We next employ a newly computed line list for the o/p-NH$_2$D transitions, where the hyperfine structure induced by both nitrogen and deuterium nuclei is included. With this new line list, the analysis of the previous spectra leads to linewidths which are compatible. Neglecting the hyperfine structure owing to D leads to overestimate the linewidths of the o/p-NH$_2$D lines at 3 mm. The error for a cold molecular core is about 50\%. This error propagates directly to the column density estimate. It is therefore recommended to take into account the hyperfine splittings caused by both the $^{14}$N and D nuclei in any analysis relying on these lines.

To date O2 has definitely been detected in only two sources, namely rho Oph A and Orion, reflecting the extremely low abundance of O2 in the interstellar medium. One of the sources in the HOP program is the +50 km/s Cloud in the Sgr A Complex in the centre of the Milky Way. The Herschel HIFI is used to search for the 487 and 774 GHz emission lines of O2. No O2 emission is detected towards the Sgr A +50 km/s Cloud, but a number of strong emission lines of methanol (CH3OH) and absorption lines of chloronium (H2Cl+) are observed. A 3 sigma upper limit for the fractional abundance ratio of (O2)/(H2) in the Sgr A +50 km/s Cloud is found to be X(O2) less than 5 x 10(-8). However, since we can find no other realistic molecular candidate than O2 itself, we very tentatively suggest that two weak absorption lines at 487.261 and 487.302 GHz may be caused by the 487 GHz line of O2 in two foreground spiral arm clouds. By considering that the absorption may only be apparent, the estimated upper limit to the O2 abundance of less than (10-20) x 10(-6) in these foreground clouds is very high. This abundance limit was determined also using Odin non-detection limits. If the absorption is due to a differential Herschel OFF-ON emission, the O2 fractional abundance may be of the order of (5-10) x 10(-6). With the assumption of pure absorption by foreground clouds, the unreasonably high abundance of (1.4-2.8) x 10(-4) was obtained. The rotation temperatures for CH3OH-A and CH3OH-E lines in the +50 km/s Cloud are found to be 64 and 79 K, respectively, and the fractional abundance of CH3OH is approximately 5 x 10(-7)., Comment: Accepted by Astronomy & Astrophysics, 11 pages, 12 figures

Cyanogen (NCCN) is the simplest member of the series of dicyanopolyynes. It has been hypothesized that this family of molecules can be important constituents of interstellar and circumstellar media, although the lack of a permanent electric dipole moment prevents its detection through radioastronomical techniques. Here we present the first solid evidence of the presence of cyanogen in interstellar clouds through the detection of its protonated form toward the cold dark clouds TMC-1 and L483. Protonated cyanogen (NCCNH+) has been identified through the J=5-4 and J=10-9 rotational transitions using the 40m radiotelescope of Yebes and the IRAM 30m telescope. We derive beam averaged column densities for NCCNH+ of (8.6+/-4.4)e10 cm-2 in TMC-1 and (3.9+/-1.8)e10 cm-2 in L483, which translate to fairly low fractional abundances relative to H2, in the range (1-10)e-12. The chemistry of protonated molecules in dark clouds is discussed, and it is found that, in general terms, the abundance ratio between the protonated and non protonated forms of a molecule increases with increasing proton affinity. Our chemical model predicts an abundance ratio NCCNH+/NCCN of 1e-4, which implies that the abundance of cyanogen in dark clouds could be as high as (1-10)e-8 relative to H2, i.e., comparable to that of other abundant nitriles such as HCN, HNC, and HC3N., Comment: Accepted for publication in A&A Letters

Small hydrocarbons, such as C2H, C3H and C3H2 are more abundant in photo-dissociation regions (PDRs) than expected based on gas-phase chemical models. To explore the hydrocarbon chemistry further, we observed a key intermediate species, the hydrocarbon ion l-C3H+, in the Horsehead PDR with the Plateau de Bure Interferometer at high-angular resolution (6''). We compare with previous observations of C2H and c-C3H2 at similar angular resolution and new gas-phase chemical model predictions to constrain the dominant formation mechanisms of small hydrocarbons in low-UV flux PDRs. We find that, at the peak of the HCO emission (PDR position), the measured l-C3H+, C2H and c-C3H2 abundances are consistent with current gas-phase model predictions. However, in the first PDR layers, at the 7.7 mum PAH band emission peak, which are more exposed to the radiation field and where the density is lower, the C2H and c-C3H2 abundances are underestimated by an order of magnitude. At this position, the l-C3H+ abundance is also underpredicted by the model but only by a factor of a few. In addition, contrary to the model predictions, l-C3H+ peaks further out in the PDR than the other hydrocarbons, C2H and c-C3H2. This cannot be explained by an excitation effect. Current gas-phase photochemical models thus cannot explain the observed abundances of hydrocarbons, in particular in the first PDR layers. Our observations are consistent with a top-down hydrocarbon chemistry, in which large polyatomic molecules or small carbonaceous grains are photo-destroyed into smaller hydrocarbon molecules/precursors., Comment: 6 pages, 3 figures, 2 tables. Accepted for publication in ApJL

Context. The increased sensitivity and high spectral resolution of millimeter telescopes allow the detection of an increasing number of isotopically substituted molecules in the interstellar medium. The 14N/ 15N ratio is difficult to measure directly for carbon containing molecules. Aims. We want to check the underlying hypothesis that the 13C/ 12C ratio of nitriles and isonitriles is equal to the elemental value via a chemical time dependent gas phase chemical model. Methods. We have built a chemical network containing D, 13C and 15N molecular species after a careful check of the possible fractionation reactions at work in the gas phase. Results. Model results obtained for 2 different physical conditions corresponding respectively to a moderately dense cloud in an early evolutionary stage and a dense depleted pre-stellar core tend to show that ammonia and its singly deuterated form are somewhat enriched in 15N, in agreement with observations. The 14N/ 15N ratio in N2H+ is found to be close to the elemental value, in contrast to previous models which obtain a significant enrichment, as we found that the fractionation reaction between 15N and N2H+ has a barrier in the entrance channel. The large values of the N2H+/15NNH+ and N2H+/ N15NH+ ratios derived in L1544 cannot be reproduced in our model. Finally we find that nitriles and isonitriles are in fact significantly depleted in 13C, questioning previous interpretations of observed C15N, HC15N and H15NC abundances from 13C containing isotopologues., Comment: 21 pages, 9 figures in the text, 3 Figures in the appendices. 7 tables in the text, 4 tables in the appendices. Accepted for publication by Astronomy Astrophysics