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The dust- and gas-rich protoplanetary disks around young stellar systems play a key role in star and planet formation. While considerable progress has recently been made in probing these disks on large scales of a few tens of astronomical units (au), the central au needs to be more investigated. We aim at unveiling the physical processes at play in the innermost regions of the strongly accreting T Tauri Star S CrA N by means of near-infrared interferometric observations. The K-band continuum emission is well reproduced with an azimuthally-modulated dusty ring. As the star alone cannot explain the size of this sublimation front, we propose that magnetospheric accretion is an important dust-heating mechanism leading to this continuum emission. The differential analysis of the Hydrogen Br$\gamma$ line is in agreement with radiative transfer models combining magnetospheric accretion and disk winds. Our observations support an origin of the Br$\gamma$ line from a combination of (variable) accretion-ejection processes in the inner disk region.

We aim to determine the $^{14}$N/$^{15}$N and $^{12}$C/$^{13}$C ratios for HCN in six starless and prestellar cores and compare the results between the direct method using radiative transfer modeling and the indirect double isotope method assuming a fixed $^{12}$C/$^{13}$C ratio. We present IRAM 30m observations of the HCN 1-0, HCN 3-2, HC15N 1-0 and H13CN 1-0 transitions toward six embedded cores. The ${}^{14}$N/${}^{15}$N ratio was derived using both the indirect double isotope method and directly through non-local thermodynamic equilibrium (NLTE) 1D radiative transfer modeling of the HCN emission. The latter also provides the ${}^{12}$C/${}^{13}$C ratio, which we compared to the local interstellar value. The derived ${}^{14}$N/${}^{15}$N ratios using the indirect method are generally in the range of 300-550. This result could suggest an evolutionary trend in the nitrogen fractionation of HCN between starless cores and later stages of the star formation process. However, the direct method reveals lower fractionation ratios of around $\sim$250, mainly resulting from a lower ${}^{12}$C/${}^{13}$C ratio in the range $\sim$20-40, as compared to the local interstellar medium value of 68. This study reveals a significant difference between the nitrogen fractionation ratio in HCN derived using direct and indirect methods. This can influence the interpretation of the chemical evolution and reveal the pitfalls of the indirect double isotope method for fractionation studies. However, the direct method is challenging, as it requires well-constrained source models to produce accurate results. No trend in the nitrogen fractionation of HCN between earlier and later stages of the star formation process is evident when the results of the direct method are considered., Comment: Accepted for publication in A&A

Within the project Evolution of Chemistry in the envelope of HOt corinoS (ECHOS), we present a study of sulphur chemistry in the envelope of the Class 0 source B335 through observations in the spectral range 7, 3, and 2 mm. We have modelled observations assuming LTE and LVG approximation. We have also used the code Nautilus to study the time evolution of sulphur species. We have detected 20 sulphur species with a total gas-phase S abundance similar to that found in the envelopes of other Class 0 objects, but with significant differences in the abundances between sulphur carbon chains and sulphur molecules containing oxygen and nitrogen. Our results highlight the nature of B335 as a source especially rich in sulphur carbon chains unlike other Class 0 sources. The low presence or absence of some molecules, such as SO and SO+, suggests a chemistry not particularly influenced by shocks. We, however, detect a large presence of HCS+ that, together with the low rotational temperatures obtained for all the S species (<15 K), reveals the moderate or low density of the envelope of B335. We also find that observations are better reproduced by models with a sulphur depletion factor of 10 with respect to the sulphur cosmic elemental abundance. The comparison between our model and observational results for B335 reveals an age of 10$^4$$<$t$<$10$^5$ yr, which highlights the particularly early evolutionary stage of this source. B335 presents a different chemistry compared to other young protostars that have formed in dense molecular clouds, which could be the result of accretion of surrounding material from the diffuse cloud onto the protostellar envelope of B335. In addition, the analysis of the SO2/C2S, SO/CS, and HCS+/CS ratios within a sample of prestellar cores and Class 0 objects show that they could be used as good chemical evolutionary indicators of the prestellar to protostellar transition.

Complex organic molecules (COMs) have been observed to be abundant in the gas phase toward protostars. Deep line surveys have been carried out only for a limited number of well-known high-mass star forming regions using the Atacama Large Millimeter/submillimeter Array (ALMA), which has unprecedented resolution and sensitivity. Statistical studies on oxygen-bearing COMs (O-COMs) in high-mass protostars using ALMA are still lacking. With the recent CoCCoA survey, we are able to determine the column density ratios of six O-COMs with respect to methanol (CH$_3$OH) in a sample of 14 high-mass protostellar sources to investigate their origin through ice and/or gas-phase chemistry. The selected species are: acetaldehyde (CH$_3$CHO), ethanol (C$_2$H$_5$OH), dimethyl ether (DME, CH$_3$OCH$_3$), methyl formate (MF, CH$_3$OCHO), glycolaldehyde (GA, CH$_2$OHCHO), and ethylene glycol (EG, (CH$_2$OH)$_2$). DME and MF have the highest and most constant ratios within one order of magnitude, while the other four species have lower ratios and exhibit larger scatter by 1-2 orders of magnitude. We compare the O-COM ratios of high-mass CoCCoA sources with those of 5 low-mass protostars available from the literature, along with the results from experiments and simulations. We find that the O-COM ratios with respect to methanol are on the same level in both the high- and low-mass samples, which suggests that these species are mainly formed in similar environments during star formation, probably in ice mantles on dust grains during early pre-stellar stages. Current simulations and experiments can reproduce most observational trends with a few exceptions, and hypotheses exist to explain the differences between observations and simulations/experiments, such as the involvement of gas-phase chemistry and different emitting areas of molecules., Comment: Accepted for publication in Astronomy & Astrophysics. 17 pages and 7 figures in the main body, 15 pages and 8 figures in the appendix

In the centre of pre-stellar cores, deuterium fractionation is enhanced due to the low temperatures and high densities. Therefore, the chemistry of deuterated molecules can be used to study the earliest stages of star formation. We analyse the deuterium fractionation of simple molecules, comparing the level of deuteration in the envelopes of the pre-stellar core L1544 in Taurus and the protostellar core HH211 in Perseus. We used single-dish observations of CCH, HCN, HNC, HCO$^+$, and their $^{13}$C-, $^{18}$O- and D-bearing isotopologues, detected with the Onsala 20m telescope. We derived the column densities and the deuterium fractions of the molecules. Additionally, we used radiative transfer simulations and results from chemical modelling to reproduce the observed molecular lines. We used new collisional rate coefficients for HNC, HN$^{13}$C, DNC, and DCN that consider the hyperfine structure of these molecules. We find high levels of deuteration for CCH (10%) in both sources, consistent with other carbon chains, and moderate levels for HCN (5-7%) and HNC (8%). The deuterium fraction of HCO$^+$ is enhanced towards HH211, most likely caused by isotope-selective photodissociation of C$^{18}$O. Similar levels of deuteration show that the process is likely equally efficient towards both cores, suggesting that the protostellar envelope still retains the chemical composition of the original pre-stellar core. The fact that the two cores are embedded in different molecular clouds also suggests that environmental conditions do not have a significant effect on the deuteration within dense cores. Radiative transfer modelling shows that it is necessary to include the outer layers of the cores to consider the effects of extended structures. Besides HCO$^+$ observations, HCN observations towards L1544 also require the presence of an outer diffuse layer where the molecules are relatively abundant., Comment: 27 pages, 17 figures, accepted for publication in A&A

Pre-stellar cores represent the earliest stage of the star- and planet-formation process. By characterizing the physical and chemical structure of these cores we can establish the initial conditions for star and planet formation and determine to what degree the chemical composition of pre-stellar cores is inherited to the later stages. A 3D MHD model of a pre-stellar core embedded in a dynamic star-forming cloud is post-processed using sequentially continuum radiative transfer, a gas-grain chemical model, and a line-radiative transfer model. Results are analyzed and compared to observations of CH$_3$OH and $c$-C$_3$H$_2$ in L1544. Nine different chemical models are compared to the observations to determine which initial conditions are compatible with the observed chemical segregation in the prototypical pre-stellar core L1544. The model is able to reproduce several aspects of the observed chemical differentiation in L1544. Extended methanol emission is shifted towards colder and more shielded regions of the core envelope while $c$-C$_3$H$_2$ emission overlaps with the dust continuum, consistent with the observed chemical structure. Increasing the strength of the interstellar radiation field or the cosmic-ray ionization rate with respect to the typical values assumed in nearby star-forming regions leads to synthetic maps that are inconsistent with the observed chemical structure. Our model shows that the observed chemical dichotomy in L1544 can arise as a result of uneven illumination due to the asymmetrical structure of the 3D core and the environment within which the core has formed. This highlights the importance of the 3D structure at the core-cloud transition on the chemistry of pre-stellar cores., Comment: Accepted for publication in A&A

The abundances of deuterated molecules with respect to their main isotopologue counterparts have been determined to be orders of magnitude higher than expected from the cosmic abundance of deuterium relative to hydrogen. The increasing number of singly and multi-deuterated species detections helps us to constrain the interplay between gas-phase and solid-state chemistry and to understand better deuterium fractionation in the early stages of star formation. Acetaldehyde is one of the most abundant complex organic molecules (COMs) in star-forming regions and its singly deuterated isotopologues have already been observed towards protostars. A spectroscopic catalogue for astrophysical purposes is built for doubly deuterated acetaldehyde CHD2CHO from measurements in the laboratory. Submillimetre wave transitions were measured for the non-rigid doubly deuterated acetaldehyde CHD2CHO displaying hindered internal rotation of its asymmetrical CHD2 methyl group. A line position analysis is carried out allowing us to reproduce 853 transition frequencies with a weighted root mean square standard deviation of 1.7, varying 40 spectroscopic constants. A spectroscopic catalogue for astrophysical purposes is built from the analysis results. Using this catalogue we were able to detect for the first time CHD2CHO towards the low-mass protostellar system IRAS 16293-2422 utilizing data from the ALMA Protostellar Interferometric Line Survey. The first detection of the CHD2CHO species allows for the derivation of its column density with a value of 1.3x10^15 cm^-2 and an uncertainty of 10-20%. The resulting D2/D ratio of ~20% is found to be coincident with D2/D ratios derived for other complex organic molecules towards IRAS~16293-2422, pointing at a common formation environment with enhanced deuterium fractionation.

Gas phase Elemental abundances in molecular CloudS (GEMS) is an IRAM 30m large program aimed at determining the elemental abundances of carbon (C), oxygen (O), nitrogen (N), and sulfur (S) in a selected set of prototypical star-forming filaments. In particular, the elemental abundance of S remains uncertain by several orders of magnitude and its determination is one of the most challenging goals of this program. We have carried out an extensive chemical modeling of the fractional abundances of CO, HCO$^+$, HCN, HNC, CS, SO, H$_2$S, OCS, and HCS$^+$ to determine the sulfur depletion toward the 244 positions in the GEMS database. These positions sample visual extinctions from A$_V$ $\sim$ 3 mag to $>$50 mag, molecular hydrogen densities ranging from a few 10$^3$~cm$^{-3}$ to 3$\times$10$^6$~cm$^{-3}$, and T$_k$ $\sim$ 10$-$35 K. Most of the positions in Taurus and Perseus are best fitted assuming early-time chemistry, t=0.1 Myr, $\zeta_{H_2}$$\sim$ (0.5$-$1)$\times$10$^{-16}$ s$^{-1}$, and [S/H]$\sim$1.5$\times$10$^{-6}$. On the contrary, most of the positions in Orion are fitted with t=1~Myr and $\zeta_{H_2}$$\sim$ 10$^{-17}$ s$^{-1}$. Moreover, $\sim$40% of the positions in Orion are best fitted assuming the undepleted sulfur abundance, [S/H]$\sim$1.5$\times$10$^{-5}$. Our results suggest that sulfur depletion depends on the environment. While the abundances of sulfur-bearing species are consistent with undepleted sulfur in Orion, a depletion factor of $\sim$20 is required to explain those observed in Taurus and Perseus. We propose that differences in the grain charge distribution in the envelopes of the studied clouds might explain these variations. The shocks associated with past and ongoing star formation could also contribute to enhance [S/H] in Orion., Comment: 22 pages, 15 figures, Astronomy and Astrophysics, in press

Aims: We aim to spatially and spectrally resolve the Br-gamma hydrogen emission line with the methods of interferometry in order to examine the kinematics of the hydrogen gas emission region in the inner accretion disk of a sample of solar-like young stellar objects. The goal is to identify trends and categories among the sources of our sample and to discuss whether or not they can be tied to different origin mechanisms associated with Br-gamma emission in T Tauri stars, chiefly and most prominently magnetospheric accretion. Methods: We observed a sample of seven T Tauri stars for the first time with VLTI GRAVITY, recording spectra and spectrally dispersed interferometric quantities across the Br-gamma line in the NIR K-band. We use them to extract the size of the Br-gamma emission region and the photocenter shifts. To assist in the interpretation, we also make use of radiative transfer models of magnetospheric accretion to establish a baseline of expected interferometric signatures if accretion is the primary driver of Br-gamma emission. Results: From among our sample, we find that five of the seven T~Tauri stars show an emission region with a half-flux radius in the range broadly expected for magnetospheric truncation. Two of the five objects also show Br-gamma emission primarily originating from within the corotation radius, while two other objects exhibit extended emission on a scale beyond 10 R$_*$, one of them even beyond the K~band continuum half-flux radius of 11.3 R$_*$. Conclusions: We find strong evidence to suggest that for the two weakest accretors in the sample, magnetospheric accretion is the primary driver of Br-gamma radiation. The results for the remaining sources imply either partial or strong contributions coming from spatially extended emission components in the form of outflows, such as stellar or disk winds., Comment: Version corresponds to the one in A&A production. The author list has been amended with "GRAVITY Collaboration" as first entry in keeping with the convention established for papers published by the GRAVITY consortium in recent years

Prestellar cores, the birthplace of Sun-like stars, form from the fragmentation of the filamentary structure that composes molecular clouds, from which they must inherit at least partially the kinematics. Furthermore, when they are on the verge of gravitational collapse, they show signs of subsonic infall motions. How extended these motions are, which depends on how the collapse occurs, remains largely unknown. We want to investigate the kinematics of the envelope that surrounds the prototypical prestellar core L1544, studying the cloud-core connection. To our aims, we observed the $\rm HCO^+$(1-0) transition in a large map. \hcop is expected to be abundant in the envelope, making it an ideal probe of the large-scale kinematics in the source. We modelled the spectrum at the dust peak by means of a non local-thermodynamical-equilibrium radiative transfer. In order to reproduce the spectrum at the dust peak, a large ($\sim 1\, \rm pc$) envelope is needed, with low density (tens of $\rm cm^{-3}$ at most) and contraction motions, with an inward velocity of $\approx 0.05\,\rm km \, s^{-1}$. We fitted the data cube using the Hill5 model, which implements a simple model {for the optical depth and excitation temperature profiles along the line-of-sight,} in order to obtain a map of the infall velocity. This shows that the infall motions are extended, with typical values in the range $0.1-0.2\,\rm km \, s^{-1}$. Our results suggest that the contraction motions extend in the diffuse envelope surrounding the core, which is consistent with recent magnetic field measurements in the source, which showed that the envelope is magnetically supercritical., Comment: Accepted for publication on ApJ, 24 Oct. 2022

We aim to quantify the effect of chemistry on the infall velocity in the prestellar core L1544. Previous observational studies have found evidence for double-peaked line profiles for the rotational transitions of several molecules, which cannot be accounted for with the models presently available for the physical structure of the source, without ad hoc up-scaling of the infall velocity. We ran one-dimensional hydrodynamical simulations of the collapse of a core with L1544-like properties (in terms of mass and outer radius), using a state-of-the-art chemical model with a very large chemical network combined with an extensive description of molecular line cooling, determined via radiative transfer simulations, with the aim of determining whether these expansions of the simulation setup (as compared to previous models) can lead to a higher infall velocity. After running a series of simulations where the simulation was sequentially simplified, we found that the infall velocity is almost independent of the size of the chemical network or the approach to line cooling. We conclude that chemical evolution does not have a large impact on the infall velocity, and that the higher infall velocities that are implied by observations may be the result of the core being more dynamically evolved than what is now thought, or alternatively the average density in the simulated core is too low. However, chemistry does have a large influence on the lifetime of the core, which varies by about a factor of two across the simulations and grows longer when the chemical network is simplified. Therefore, although the model is subject to several sources of uncertainties, the present results clearly indicate that the use of a small chemical network leads to an incorrect estimate of the core lifetime, which is naturally a critical parameter for the development of chemical complexity in the precollapse phase., Comment: 12 pages incl. Appendix; 8 figures; accepted to A&A; replacement to reflect the change of the title of the paper post-acceptance

Spectral line profiles of several molecules observed towards the pre-stellar core L1544 appear double-peaked. For abundant molecular species this line morphology has been linked to self-absorption. However, the physical process behind the double-peaked morphology for less abundant species is still under debate. In order to understand the cause behind the double-peaked spectra of optically thin transitions and their link to the physical structure of pre-stellar cores, we present high-sensitivity and high-spectral resolution HC$^{17}$O$^+$ $J =$1-0 observations towards the dust peak in L1544. We observed the HC$^{17}$O$^+$ (1-0) spectrum with the Institut de Radioastronomie Millim\'etrique (IRAM) 30m telescope. By using new state-of-the-art collisional rate coefficients, a physical model for the core and the fractional abundance profile of HC$^{17}$O$^+$, the hyperfine structure of this molecular ion is modelled for the first time with the radiative transfer code LOC applied to the predicted chemical structure of a contracting pre-stellar core. We applied the same analysis to the chemically related C$^{17}$O molecule. The observed HC$^{17}$O$^+$(1-0) and C$^{17}$O(1-0) lines have been successfully reproduced with a non-local thermal equilibrium (LTE) radiative transfer model applied to chemical model predictions for a contracting pre-stellar core. An upscaled velocity profile (by 30%) is needed to reproduce the HC$^{17}$O$^+$(1-0) observations. The double peaks observed in the HC$^{17}$O$^+$(1-0) hyperfine components are due to the contraction motions at densities close to the critical density of the transition ($\sim$10$^{5}$ cm$^{-3}$) and to the fact that the HCO$^{+}$ fractional abundance decreases toward the centre.

Context: In the centre of pre-stellar cores, the deuterium fractionation is enhanced due to the cold temperatures and high densities. Therefore, the chemistry of deuterated molecules can be used to probe the evolution and the kinematics in the earliest stages of star formation. Aims: We analyse emission maps of cyclopropenylidene, c-C$_3$H$_2$, to study the distribution of the deuteration throughout the prototypical pre-stellar core L1544. Methods: We use single-dish observations of c-C$_3$H$_2$, c-H$^{13}$CC$_2$H, c-C$_3$HD, and c-C$_3$D$_2$ towards the pre-stellar core L1544, performed at the IRAM 30m telescope. We derive the column density and deuterium fraction maps, and compare these observations with non-LTE radiative transfer simulations. Results: The highest deuterium fractions are found close to the dust peak at the centre of L1544, where the increased abundance of H$_2$D$^+$ ions drives the deuteration process. The peak values are N(c-C$_3$HD)/N(c-C$_3$H$_2)=0.17\pm0.01$, N(c-C$_3$D$_2$)/N(c-C$_3$H$_2)=0.025\pm0.003$ and N(c-C$_3$D$_2$)/N(c-C$_3$HD$)=0.16\pm0.03$, which is consistent with previous single point observations. The distributions of c-C$_3$HD and c-C$_3$D$_2$ indicate that the deuterated forms of c-C$_3$H$_2$ in fact trace the dust peak and not the c-C$_3$H$_2$ peak. Conclusions: The N(c-C$_3$D$_2$)/N(c-C$_3$HD) map confirms that the process of deuteration is more efficient towards the centre of the core and demonstrates that carbon-chain molecules are still present at high densities. This is likely caused by an increased abundance of He$^+$ ions destroying CO, which increases the amount of carbon atoms in the gas phase., Comment: 13 pages, 9 figures

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

Protostellar jets are an important agent of star formation feedback, tightly connected with the mass-accretion process. The history of jet formation and mass-ejection provides constraints on the mass accretion history and the nature of the driving source. We want to characterize the time-variability of the mass-ejection phenomena at work in the Class 0 protostellar phase, in order to better understand the dynamics of the outflowing gas and bring more constraints on the origin of the jet chemical composition and the mass-accretion history. We have observed the emission of the CO 2-1 and SO N_J=5_4-4_3 rotational transitions with NOEMA, towards the intermediate-mass Class 0 protostellar system Cep E. The CO high-velocity jet emission reveals a central component associated with high-velocity molecular knots, also detected in SO, surrounded by a collimated layer of entrained gas. The gas layer appears to accelerate along the main axis over a length scale delta_0 ~700 au, while its diameter gradually increases up to several 1000au at 2000au from the protostar. The jet is fragmented into 18 knots of mass ~10^-3 Msun, unevenly distributed between the northern and southern lobes, with velocity variations up to 15 km/s close to the protostar, well below the jet terminal velocities. The knot interval distribution is approximately bimodal with a scale of ~50-80yr close to the protostar and ~150-200yr at larger distances >12". The mass-loss rates derived from knot masses are overall steady, with values of 2.7x10^-5 Msun/yr (8.9x10^-6 Msun/yr) in the northern (southern) lobe. The interaction of the ambient protostellar material with high-velocity knots drives the formation of a molecular layer around the jet, which accounts for the higher mass-loss rate in the north. The jet dynamics are well accounted for by a simple precession model with a period of 2000yr and a mass-ejection period of 55yr., Comment: 13 pages, 9 figures, 3 table. Accepted in A&A

Deuteration is a crucial tool to understand the complexity of interstellar chemical processes, especially when they involve the interplay of gas-phase and grain-surface chemistry. In the case of multiple deuteration, comparing observation with the results of chemical modelling is particularly effective to study how molecules are inherited in the different stages within the process of star and planet formation. We aim to study the the D/ H ratio in H2CS across the prototypical pre-stellar core L1544. This study allows us to test current gas-dust chemical models involving sulfur in dense cores. We present here single-dish observations of H2CS, HDCS and D2CS with the IRAM 30m telescope. We analyse their column densities and distributions, and compare these observations with gas-grain chemical models. The deuteration maps of H2CS in L1544 are compared with the deuteration maps of methanol, H2CO, N2H+ and HCO+ towards the same source. Furthermore, the single and double deuteration of H2CS towards the dust peak of L1544 is compared with H2CO and c-C3H2. The difference between the deuteration of these molecules in L1544 is discussed and compared with the prediction of chemical models. The maximum deuterium fractionation for the first deuteration of H2CS is N(HDCS)/N(H2CS)$\sim$30$\%$ and is located towards the north-east at a distance of about 10000 AU from the dust peak. While for c-C3H2 the first and second deuteration have a similar efficiency, for H2CS and H2CO the second deuteration is more efficient, leading to D2CX/HDCX$\sim$100$\%$ (with X= O or S). Our results imply that the large deuteration of H2CO and H2CS observed in protostellar cores as well as in comets is likely inherited from the pre-stellar phase. However, the comparison with state-of-the-art chemical models suggests that the reaction network for the formation of the doubly deuterated H2CS and H2CO it is not complete yet., Comment: Accepted for publication in A&A

Methanol, one of the simplest complex organic molecules in the Interstellar Medium (ISM), has been shown to be present and extended in cold environments such as starless cores. We aim at studying methanol emission across several starless cores and investigate the physical conditions at which methanol starts to be efficiently formed, as well as how the physical structure of the cores and their surrounding environment affect its distribution. Methanol and C$^{18}$O emission lines at 3 mm have been observed with the IRAM 30m telescope within the large program "Gas phase Elemental abundances in Molecular CloudS" (GEMS) towards 66 positions across 12 starless cores in the Taurus Molecular Cloud. A non-LTE radiative transfer code was used to compute the column densities in all positions. We then used state-of-the-art chemical models to reproduce our observations. We have computed N(CH$_3$OH)/N(C$^{18}$O) column density ratios for all the observed offsets, and two different behaviours can be recognised: the cores where the ratio peaks at the dust peak, and the cores where the ratio peaks with a slight offset with respect to the dust peak ($\sim $10000 AU). We suggest that the cause of this behaviour is the irradiation on the cores due to protostars nearby which accelerate energetic particles along their outflows. The chemical models, which do not take into account irradiation variations, can reproduce fairly well the overall observed column density of methanol, but cannot reproduce the two different radial profiles observed. We confirm the substantial effect of the environment onto the distribution of methanol in starless cores. We suggest that the clumpy medium generated by protostellar outflows might cause a more efficient penetration of the interstellar radiation field in the molecular cloud and have an impact on the distribution of methanol in starless cores., Comment: Accepted for publication in A&A

Under cold conditions in dense cores, gas-phase molecules and atoms are depleted from the gas-phase to the surface of interstellar grains. Considering the time scales and physical conditions within these cores, a portion of these molecules has to be brought back into the gas-phase to explain their observation by milimeter telescopes. We tested the respective efficiencies of the different mechanisms commonly included in the models. We also tested the addition of sputtering of ice grain mantles via a collision with cosmic rays in the electronic stopping power regime. The ice sputtering induced by cosmic rays has been added to the Nautilus gas-grain model while the other processes were already present. Each of these processes were tested on a 1D physical structure determined by observations in TMC1 cold cores. The resulting 1D chemical structure was also compared to methanol gas-phase abundances observed in these cores. We found that all species are not sensitive in the same way to the non-thermal desorption mechanisms, and the sensitivity also depends on the physical conditions. Thus, it is mandatory to include all of them. Chemical desorption seems to be essential in reproducing the observations for H densities smaller than $4\times 10^4$~cm$^{-3}$, whereas sputtering is essential above this density. The models are, however, systematically below the observed methanol abundances. A more efficient chemical desorption and a more efficient sputtering could better reproduce the observations. In conclusion, the sputtering of ices by cosmic-rays collisions may be the most efficient desorption mechanism at high density (a few $10^4$~cm$^{-3}$ under the conditions studied here) in cold cores, whereas chemical desorption is still required at smaller densities. Additional works are needed on both mechanisms to assess their efficiency with respect to the main ice composition., 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

The isotopic ratio of nitrogen presents a wide range of values in the Solar System and in star forming system whose origin is still unclear. Chemical reactions in the gas phase are one of the possible processes that could modify the $^{14}$N/$^{15}$N ratio. We aim at investigating if and how the passage of a shock wave in the interstellar medium, can affect the relative fraction of nitrogen isotopes. The ideal place for such a study is the L1157 outflow, where several shocked clumps are present. We present the first measurement of the $^{14}$N/$^{15}$N ratio in the two shocked clumps, B1 and B0, of the protostellar outflow L1157, derived from the interferomteric maps of the H$^{13}$CN(1-0) and the HC$^{15}$N(1-0) lines. In B1, we find that the H$^{13}$CN(1-0) and HC$^{15}$N(1-0) emission traces the front of the clump, with averaged column density of $N$(H$^{13}$CN) $\sim$ 7$\times$10$^{12}$ cm$^{-2}$ and $N$(HC$^{15}$N) $\sim$ 2$\times$10$^{12}$ cm$^{-2}$. In this region the ratio H$^{13}$CN(1-0)/HC$^{15}$N(1-0) is quite uniform with an average value of $\sim$ 5$\pm$1. The same average value is also measured in the smaller clump B0e. Assuming the standard $^{12}$C/$^{13}$C = 68, we obtain $^{14}$N/$^{15}$N = 340$\pm$70, similar to those usually found in prestellar cores and protostars. We analysed the prediction of a chemical shock model for several shock conditions and we found that the nitrogen and carbon fractionations do not vary much for the first period after the shock. The observed H$^{13}$CN/HC$^{15}$N can be reproduced by a non-dissociative, C-type shock with parameters in agreement with previous modelling of L1157-B1. Both observations and chemical models indicate that the shock propagation does not affect the nitrogen isotopic ratio that remains similar to that measured in lower temperature gas in prestellar cores and in protostellar envelopes., Comment: 7 pages, 6 figures

Context. The spatial distribution of molecules around starless cores is a powerful tool for studying the physics and chemistry governing the earliest stages of star formation. Aims. Our aim is to study the chemical differentiation in starless cores to determine the influence of large-scale effects on the spatial distribution of molecules within the cores. Furthermore, we want to put observational constraints on the mechanisms responsible in starless cores for the desorption of methanol from the surface of dust grains where it is efficiently produced. Methods. We mapped methanol, CH3OH, and cyclopropenylidene, c-C3H2, with the IRAM 30m telescope in the 3 mm band towards six starless cores embedded in different environments, and in different evolutionary stages. Furthermore, we searched for correlations among physical properties of the cores and the methanol distribution. Results. From our maps we can infer that the chemical segregation between CH3OH and c-C3H2 is driven by uneven illumination from the interstellar radiation field (ISRF). The side of the core that is more illuminated has more C atoms in the gas-phase and the formation of carbon-chain molecules like c-C3H2 is enhanced. Instead, on the side that is less exposed to the ISRF the C atoms are mostly locked in carbon monoxide, CO, the precursor of methanol. Conclusions. We conclude that large-scale effects have a direct impact on the chemical segregation that we can observe at core scale. However, the non-thermal mechanisms responsible for the desorption of methanol in starless cores do not show any dependency on the H2 column density at the methanol peak., Comment: Accepted for publication in A&A

L1157-B1 is one of the outflow shocked regions along the blue-shifted outflow driven by the Class 0 protostar L1157-mm, and is an ideal laboratory to study the material ejected from the grains in very short timescales, i.e. its chemical composition is representative of the composition of the grains. We imaged $^{28}$SiO, $^{29}$SiO and $^{30}$SiO J = 2-1 emission towards L1157-B1 and B0 with the NOrthern Extended Millimeter Array (NOEMA) interferometer as part of the Seeds of Life in Space (SOLIS) large project. We present here a study of the isotopic fractionation of SiO towards L1157-B1. Furthermore, we use the high spectral resolution observations on the main isotopologue, $^{28}$SiO, to study the jet impact on the dense gas. We present here also single-dish observations obtained with the IRAM 30m telescope and Herschel-HIFI. We carried out a non-LTE analysis using a Large Velocity Gradient (LVG) code to model the single-dish observations. From our observations we can show that (i) the (2-1) transition of the main isotopologue is optically thick in L1157-B1 even at high velocities, and (ii) the [$^{29}$SiO/$^{30}$SiO] ratio is constant across the source, and consistent with the solar value of 1.5. We report the first isotopic fractionation maps of SiO in a shocked region and show the absence of a mass dependent fractionation in $^{29}$Si and $^{30}$Si across L1157-B1. A high-velocity bullet in $^{28}$SiO has been identified, showing the signature of a jet impacting on the dense gas. With the dataset presented in this paper, both interferometric and single-dish, we were able to study in great detail the gas shocked at the B1a position and its surrounding gas., Comment: Accepted for publication in A&A

The SOLIS (Seeds Of Life In Space) IRAM/NOEMA Large Program aims at studying a set of crucial complex organic molecules in a sample of sources, with well-known physical structure, covering the various phases of Solar-type star formation. One representative object of the transition from the prestellar core to the protostar phases has been observed toward the Very Low Luminosity Object (VeLLO) called L1521F. This type of source is important to study to make the link between prestellar cores and Class 0 sources and also to constrain the chemical evolution during the process of star formation. Two frequency windows (81.6-82.6 GHz and 96.65-97.65 GHz) were used to observe the emission from several complex organics toward the L1521F VeLLO. Only 2 transitions of methanol (A+, E2) have been detected in the narrow window centered at 96.7 GHz (with an upper limit on E1) in a very compact emission blob (~7'' corresponding to ~1000au) toward the NE of the L1521F protostar. The CS 2-1 transition is also detected within the WideX bandwidth. Consistently, with what has been found in prestellar cores, the methanol emission appears ~1000au away from the dust peak. The location of the methanol blob coincides with one of the filaments previously reported in the literature. The Tex of the gas inferred from methanol is (10$\pm$2) K, while the H2 gas density (estimated from the detected CS 2-1 emission and previous CS 5-4 ALMA obs.) is a factor >25 higher than the density in the surrounding environment (n(H2) >10$^{7}$ cm$^{-3}$). From its compactness, low excitation temperature and high gas density, we suggest that the methanol emission detected with NOEMA is either a cold and dense shock-induced blob, recently formed ($\leq$ few hundred years) by infalling gas or a cold and dense fragment that may have just been formed as a result of the intense gas dynamics found within the L1521F VeLLO system., Comment: 11 pages, 7 figures, 3 tables, accepted for publication by A&A

Aim: In the past, observations of protostellar shocks have been able to set constraints on the formation route of formamide (NH2CHO), exploiting its observed spatial distribution and comparison with astrochemical model predictions. In this work, we follow the same strategy to study the case of acetaldehyde (CH3CHO). Method: To this end, we used the data obtained with the IRAM-NOEMA interferometer in the framework of the Large Program SOLIS to image the B0 and B1 shocks along the L1157 blueshifted outflow in methanol (CH3OH) and acetaldehyde line emission. Results: We imaged six CH3OH and eight CH3CHO lines which cover upper level energies up to 30 K. Both species trace the B0 molecular cavity as well as the northern B1 portion, i.e. the regions where the youngest shocks (1000 yr) occurred. The CH$_3$OH and CH$_3$CHO emission peaks towards the B1b clump, where we measured the following column densities and relative abundances: 1.3 x 10^16 cm-2 and 6.5 x 10-6 (methanol), and 7 x 10^13 cm-2 and 3.5 x 10-8 (acetaldehyde). We carried out a non-LTE LVG analysis of the observed CH3OH line: the average kinetic temperature and density of the emitting gas are Tkin = 90 K and nH2 = 4 x 10^5 cm-3, respectively. The CH3OH and CH3CHO abundance ratio towards B1b is 190, varying by less than a factor 3 throughout the whole B0-B1 structure. Conclusions: The comparison of astrochemical model predictions with the observed methanol and acetaldehyde spatial distribution does not allow to distinguish whether acetaldehyde is formed on the grain mantles or rather on the gas-phase, as its gas-phase formation, dominated by the reaction of ethyl radical (CH3CH2) with atomic oxygen, is very fast. Observations of acetaldehyde in younger shocks, e.g. 10^2 yr old, or/and of the ethyl radical, whose frequencies are not presently available, are necessary to settle the issue., Comment: A&A, in press

L1521E is a dense starless core in Taurus that was found to have relatively low molecular depletion by earlier studies, thus suggesting a recent formation. We aim to characterize the chemical structure of L1521E and compare it to the more evolved L1544 pre-stellar core. We have obtained $\sim$2.5$\times$2.5 arcminute maps toward L1521E using the IRAM-30m telescope in transitions of various species. We derived abundances for the species and compared them to those obtained toward L1544. We estimated CO depletion factors. Similarly to L1544, $c$-C$_3$H$_2$ and CH$_3$OH peak at different positions. Most species peak toward the $c$-C$_3$H$_2$ peak. The CO depletion factor derived toward the $Herschel$ dust peak is 4.3$\pm$1.6, which is about a factor of three lower than that toward L1544. The abundances of sulfur-bearing molecules are higher toward L1521E than toward L1544 by factors of $\sim$2-20. The abundance of methanol is similar toward the two cores. The higher abundances of sulfur-bearing species toward L1521E than toward L1544 suggest that significant sulfur depletion takes place during the dynamical evolution of dense cores, from the starless to pre-stellar stage. The CO depletion factor measured toward L1521E suggests that CO is more depleted than previously found. Similar CH$_3$OH abundances between L1521E and L1544 hint that methanol is forming at specific physical conditions in Taurus, characterized by densities of a few $\times$10$^4$ cm$^{-3}$ and $N$(H$_2$)$\gtrsim$10$^{22}$ cm$^{-2}$, when CO starts to catastrophically freeze-out, while water can still be significantly photodissociated, so that the surfaces of dust grains become rich in solid CO and CH$_3$OH, as already found toward L1544. Methanol can thus provide selective crucial information about the transition region between dense cores and the surrounding parent cloud., Comment: Accepted for publication in A&A, abstract abridged

The ketenyl radical, HCCO, has recently been detected in the ISM for the first time. Further astronomical detections of HCCO will help us understand its gas-grain chemistry, and subsequently revise the oxygen-bearing chemistry towards dark clouds. Moreover, its deuterated counterpart, DCCO, has never been observed in the ISM. HCCO and DCCO still lack a broad spectroscopic investigation, although they exhibit a significant astrophysical relevance. In this work we aim to measure the pure rotational spectra of the ground state of HCCO and DCCO in the millimeter and submillimeter region, considerably extending the frequency range covered by previous studies. The spectral acquisition was performed using a frequency-modulation absorption spectrometer between 170 and 650 GHz. The radicals were produced in a low-density plasma generated from a select mixture of gaseous precursors. For each isotopologue we were able to detect and assign more than 100 rotational lines. The new lines have significantly enhanced the previous data set allowing the determination of highly precise rotational and centrifugal distortion parameters. In our analysis we have taken into account the interaction between the ground electronic state and a low-lying excited state (Renner-Teller pair) which enables the prediction and assignment of rotational transitions with $K_a$ up to 4. The present set of spectroscopic parameters provides highly accurate, millimeter and submillimeter rest-frequencies of HCCO and DCCO for future astronomical observations. We also show that towards the pre-stellar core L1544, ketenyl peaks in the region where $c$-$\mathrm{C_3H_2}$ peaks, suggesting that HCCO follows a predominant hydrocarbon chemistry, as already proposed by recent gas-grain chemical models.

The study of deuteration in pre-stellar cores is important to understand the physical and chemical initial conditions in the process of star formation. In particular, observations toward pre-stellar cores of methanol and deuterated methanol, solely formed on the surface of dust grains, may provide useful insights on surface processes at low temperatures. Here we analyze maps of CO, methanol, formaldehyde and their deuterated isotopologues toward a well-known pre-stellar core. This study allows us to test current gas-dust chemical models. Single-dish observations of CH$_3$OH, CH$_2$DOH, H$_2$CO, H$_2\,^{13}$CO, HDCO, D$_2$CO and C$^{17}$O toward the prototypical pre-stellar core L1544 were performed at the IRAM 30 m telescope. We analyze their column densities, distributions, and compare these observations with gas-grain chemical models. The maximum deuterium fraction derived for methanol is [CH$_2$DOH]/[CH$_3$OH] $\sim$ 0.08$\pm$0.02, while the measured deuterium fractions of formaldehyde at the dust peak are [HDCO]/[H$_2$CO] $\sim$ 0.03$\pm$0.02, [D$_2$CO]/[H$_2$CO] $\sim$ 0.04$\pm$0.03 and [D$_2$CO]/[HDCO] $\sim$ 1.2$\pm$0.3. Observations differ significantly from the predictions of models, finding discrepancies between a factor of 10 and a factor of 100 in most cases. It is clear though that to efficiently produce methanol on the surface of dust grains, quantum tunneling diffusion of H atoms must be switched on. It also appears that the currently adopted reactive desorption efficiency of methanol is overestimated and/or that abstraction reactions play an important role. More laboratory work is needed to shed light on the chemistry of methanol, an important precursor of complex organic molecules in space., Comment: Accepted for publication in A&A

We use the deuteration of $c$-$\mathrm{C_{3}H_{2}}$ to probe the physical parameters of starless and protostellar cores, related to their evolutionary states, and compare it to the $\mathrm{N_{2}H^{+}}$-deuteration in order to study possible differences between the deuteration of C- and N-bearing species. We observed the main species $c$-$\mathrm{C_{3}H_{2}}$, the singly and doubly deuterated species $c$-$\mathrm{C_{3}HD}$ and $c$-$\mathrm{C_{3}D_{2}}$, as well as the isotopologue $c$-$\mathrm{{H^{13}CC_{2}H}}$ toward 10 starless cores and 5 protostars in the Taurus and Perseus Complexes. We examined the correlation between the $N$($c$-$\mathrm{C_{3}HD}$)/$N$($c$-$\mathrm{C_{3}H_{2}}$) ratio and the dust temperature along with the $\mathrm{H_2}$ column density and the CO depletion factor. The resulting $N$($c$-$\mathrm{C_{3}HD}$)/$N$($c$-$\mathrm{C_{3}H_{2}}$) ratio is within the error bars consistent with $10\%$ in all starless cores with detected $c$-$\mathrm{C_{3}HD}$. This also accounts for the protostars except for the source HH211, where we measure a high deuteration level of $23\%$. The deuteration of $\mathrm{N_{2}H^{+}}$ follows the same trend but is considerably higher in the dynamically evolved core L1544. Toward the protostellar cores the coolest objects show the largest deuterium fraction in $c$-$\mathrm{C_{3}H_{2}}$. We show that the deuteration of $c$-$\mathrm{C_{3}H_{2}}$ can trace the early phases of star formation and is comparable to that of $\mathrm{N_{2}H^{+}}$. However, the largest $c$-$\mathrm{C_{3}H_{2}}$ deuteration level is found toward protostellar cores, suggesting that while $c$-$\mathrm{C_{3}H_{2}}$ is mainly frozen onto dust grains in the central regions of starless cores, active deuteration is taking place on ice.

A better understanding of sulphur chemistry is needed to solve the interstellar sulphur depletion problem. A way to achieve this goal is to study new S-bearing molecules in the laboratory, obtaining accurate rest frequencies for an astronomical search. We focus on dithioformic acid, HCSSH, which is the sulphur analogue of formic acid. The aim of this study is to provide an accurate line list of the two HCSSH $trans$ and $cis$ isomers in their electronic ground state and a comprehensive centrifugal distortion analysis with an extension of measurements in the millimetre and submillimetre range. We studied the two isomers in the laboratory using an absorption spectrometer employing the frequency-modulation technique. The molecules were produced directly within a free-space cell by glow discharge of a gas mixture. We measured lines belonging to the electronic ground state up to 478 GHz, with a total number of 204 and 139 new rotational transitions, respectively, for $trans$ and $cis$ isomers. The final dataset also includes lines in the centimetre range available from literature. The extension of the measurements in the mm and submm range lead to an accurate set of rotational and centrifugal distortion parameters. This allows us to predict frequencies with estimated uncertainties as low as 5 kHz at 1 mm wavelength. Hence, the new dataset provided by this study can be used for astronomical search.

Complex organic molecules have been observed for decades in the interstellar medium. Some of them might be considered as small bricks of the macromolecules at the base of terrestrial life. It is hence particularly important to understand organic chemistry in Solar-like star forming regions. In this article, we present a new observational project: SOLIS (Seeds Of Life In Space). This is a Large Project at the IRAM-NOEMA interferometer, and its scope is to image the emission of several crucial organic molecules in a sample of Solar-like star forming regions in different evolutionary stage and environments. Here, we report the first SOLIS results, obtained from analysing the spectra of different regions of the Class 0 source NGC1333-IRAS4A, the protocluster OMC-2 FIR4, and the shock site L1157-B1. The different regions were identified based on the images of formamide (NH2CHO) and cyanodiacetylene (HC5N) lines. We discuss the observed large diversity in the molecular and organic content, both on large (3000-10000 au) and relatively small (300-1000 au) scales. Finally, we derive upper limits to the methoxy fractional abundance in the three observed regions of the same order of magnitude of that measured in few cold prestellar objects, namely ~10^-12-10^-11 with respect to H2 molecules., Comment: Accepted for publication on The Astrophysical Journal

Context: Modern versions of the Miller-Urey experiment claim that formamide (NH$_2$CHO) could be the starting point for the formation of metabolic and genetic macromolecules. Intriguingly, formamide is indeed observed in regions forming Solar-type stars as well as in external galaxies. Aims: How NH$_2$CHO is formed has been a puzzle for decades: our goal is to contribute to the hotly debated question of whether formamide is mostly formed via gas-phase or grain surface chemistry. Methods: We used the NOEMA interferometer to image NH$_2$CHO towards the L1157-B1 blue-shifted shock, a well known interstellar laboratory, to study how the components of dust mantles and cores released into the gas phase triggers the formation of formamide. Results: We report the first spatially resolved image (size $\sim$ 9", $\sim$ 2300 AU) of formamide emission in a shocked region around a Sun-like protostar: the line profiles are blueshifted and have a FWHM $\simeq$ 5 km s$^{-1}$. A column density of $N_{\rm NH_2CHO}$ = 8 $\times$ 10$^{12}$ cm$^{-1}$, and an abundance (with respect to H-nuclei) of 4 $\times$ 10$^{-9}$ are derived. We show a spatial segregation of formamide with respect to other organic species. Our observations, coupled with a chemical modelling analysis, indicate that the formamide observed in L1157-B1 is formed by gas-phase chemical process, and not on grain surfaces as previously suggested. Conclusions: The SOLIS interferometric observations of formamide provide direct evidence that this potentially crucial brick of life is efficiently formed in the gas-phase around Sun-like protostars., Comment: 7 pages, 1 table, 5 figures, A&A Letters, in press

Prior to star formation, pre-stellar cores accumulate matter towards the centre. As a consequence, their central density increases while the temperature decreases. Understanding the evolution of the chemistry and physics in this early phase is crucial to study the processes governing the formation of a star. We aim at studying the chemical differentiation of a prototypical pre-stellar core, L1544, by detailed molecular maps. In contrast with single pointing observations, we performed a deep study on the dependencies of chemistry on physical and external conditions. We present the emission maps of 39 different molecular transitions belonging to 22 different molecules in the central 6.25 arcmin$^2$ of L1544. We classified our sample in five families, depending on the location of their emission peaks within the core. Furthermore, to systematically study the correlations among different molecules, we have performed the principal component analysis (PCA) on the integrated emission maps. The PCA allows us to reduce the amount of variables in our dataset. Finally, we compare the maps of the first three principal components with the H$_2$ column density map, and the T$_{dust}$ map of the core. The results of our qualitative analysis is the classification of the molecules in our dataset in the following groups: (i) the $c$-C$_3$H$_2$ family (carbon chain molecules), (ii) the dust peak family (nitrogen-bearing species), (iii) the methanol peak family (oxygen-bearing molecules), (iv) the HNCO peak family (HNCO, propyne and its deuterated isotopologues). Only HC$^{18}$O$^+$ and $^{13}$CS do not belong to any of the above mentioned groups. The principal component maps allow us to confirm the (anti-)correlations among different families that were described in a first qualitative analysis, but also points out the correlation that could not be inferred before., Comment: 29 pages, 19 figures, 2 appendices, accepted for publication in A&A, arXiv abstract has been slightly modified

The interstellar delivery of carbon atoms locked into molecules might be one of the key ingredients for the emergence of life. Cyanopolyynes are carbon chains delimited at their two extremities by an atom of hydrogen and a cyano group, so that they might be excellent reservoirs of carbon. The simplest member, HC3N, is ubiquitous in the galactic interstellar medium and found also in external galaxies. Thus, understanding the growth of cyanopolyynes in regions forming stars similar to our Sun, and what affects it, is particularly relevant. In the framework of the IRAM/NOEMA Large Program SOLIS (Seeds Of Life In Space), we have obtained a map of two cyanopolyynes, HC3N and HC5N, in the protocluster OMC2-FIR4. Because our Sun is thought to be born in a rich cluster, OMC2-FIR4 is one of the closest and best known representatives of the environment in which the Sun may have been born. We find a HC3N/HC5N abundance ratio across the source in the range ~ 1 - 30, with the smallest values (< 10) in FIR5 and in the Eastern region of FIR4. The ratios < 10 can be reproduced by chemical models only if: (1) the cosmic-ray ionisation rate $\zeta$ is ~ $4 \times 10^{-14}$ s$^{-1}$; (2) the gaseous elemental ratio C/O is close to unity; (3) O and C are largely depleted. The large $\zeta$ is comparable to that measured in FIR4 by previous works and was interpreted as due to a flux of energetic (> 10 MeV) particles from embedded sources. We suggest that these sources could lie East of FIR4 and FIR5. A temperature gradient across FIR4, with T decreasing by about 10 K, could also explain the observed change in the HC3N/HC5N line ratio, without the need of a cosmic ray ionisation rate gradient. However, even in this case, a high constant cosmic-ray ionisation rate (of the order of $10^{-14}$ s$^{-1}$) is necessary to reproduce the observations., Comment: 12 pages, 8 figures, accepted for publication in A&A

Aims. We aim to understand the high cyclic-to-linear $\rm C_3H_2$ ratio ($32 \pm 4$) observed toward L1544 by Spezzano et al. (2016). Methods. We combine a gas-grain chemical model with a physical model for L1544 to simulate the column densities of cyclic and linear $\rm C_3H_2$ observed toward L1544. The most important reactions for the formation and destruction of both forms of $\rm C_3H_2$ are identified, and their relative rate coefficients are varied to find the best match to the observations. Results. We find that the ratio of the rate coefficients of $\rm C_3H_3^+ + e^- \longrightarrow C_3H_2 + H$ for cyclic and linear $\rm C_3H_2$ must be $\sim 20$ in order to reproduce the observations, depending on the branching ratios assumed for the $\rm C_3H_3^+ + e^- \longrightarrow C_3H + H_2$ reaction. In current astrochemical networks it is assumed that cyclic and linear $\rm C_3H_2$ are formed in a 1:1 ratio in the aforementioned reactions. Laboratory studies and/or theoretical calculations are needed to confirm the results of our chemical modeling based on observational constraints., Comment: 5 pages, 2 figures; accepted as an A&A Letter

The partially deuterated linear isomer HDCCC of the ubiquitous cyclic carbene ($c$-C$_3$H$_2$) was observed in the starless cores TMC-1C and L1544 at 96.9 GHz, and a confirming line was observed in TMC-1 at 19.38 GHz. To aid the identification in these narrow line sources, four centimetre-wave rotational transitions (two in the previously reported $K_a =0$ ladder, and two new ones in the $K_a =1$ ladder), and 23 transitions in the millimetre band between 96 and 272 GHz were measured in high-resolution laboratory spectra. Nine spectroscopic constants in a standard asymmetric top Hamiltonian allow the principal transitions of astronomical interest in the $K_a \le 3$ rotational ladders to be calculated to within 0.1 km s$^{-1}$ in radial velocity up to 400 GHz. Conclusive evidence for the identification of the two astronomical lines of HDCCC was provided by the $V_{\rm{LSR}}$ which is the same as that of the normal isotopic species (H$_2$CCC) in the three narrow line sources. In these sources, deuterium fractionation in singly substituted H$_2$CCC (HDCCC/H$_2$CCC $\sim4\%\text{-}19\%$) is comparable to that in $c$-C$_3$H$_2$ ($c$-C$_3$H$_2$/$c$-C$_3$HD $\sim5\%\text{-}17\%$), and similarly in doubly deuterated $c$-C$_3$H$_2$ ($c$-C$_3$D$_2$/$c$-C$_3$HD $\sim3\%\text{-}17\%$), implying that the efficiency of the deuteration processes in the H$_2$CCC and $c$-C$_3$H$_2$ isomers are comparable in dark clouds., Comment: Accepted for publication in A&A

Orion KL has served as a benchmark for spectral line searches throughout the (sub)millimeter regime. The main goal is to systematically study spectral characteristics of Orion KL in the 1.3 cm band. We carried out a spectral line survey (17.9 GHz to 26.2 GHz) with the Effelsberg-100 m telescope towards Orion KL. We find 261 spectral lines, yielding an average line density of about 32 spectral features per GHz above 3$\sigma$. The identified lines include 164 radio recombination lines (RRLs) and 97 molecular lines. A total of 23 molecular transitions from species known to exist in Orion KL are detected for the first time in the interstellar medium. Non-metastable 15NH3 transitions are detected in Orion KL for the first time. Based on the velocity information of detected lines and the ALMA images, the spatial origins of molecular emission are constrained and discussed. A narrow feature is found in SO2 ($8_{1,7}-7_{2,6}$), possibly suggesting the presence of a maser line. Column densities and fractional abundances relative to H2 are estimated for 12 molecules with LTE methods. Rotational diagrams of non-metastable 14NH3 transitions with J=K+1 to J=K+4 yield different results; metastable 15NH3 is found to have a higher excitation temperature than non-metastable 15NH3, indicating that they may trace different regions. Elemental and isotopic abundance ratios are estimated: 12C/13C=63+-17, 14N/15N=100+-51, D/H=0.0083+-0.0045. The dispersion of the He/H ratios derived from H$\alpha$/He$\alpha$ pairs to H$\delta$/He$\delta$ pairs is very small, which is consistent with theoretical predictions that the departure coefficients bn factors for hydrogen and helium are nearly identical. Based on a non-LTE code neglecting excitation by the infrared radiation field and a likelihood analysis, we find that the denser regions have lower kinetic temperature, which favors an external heating of the Hot Core., Comment: 70 pages, 26 figures, 12 tables, accepted for publication in A&A. Figs. 1, 2, 8, 9 have been downsized

IRC +10216 is the prototypical carbon star exhibiting an extended molecular circumstellar envelope. Its spectral properties are therefore the template for an entire class of objects. The main goal is to systematically study the $\lambda$ $\sim$1.3 cm spectral line characteristics of IRC +10216. We carried out a spectral line survey with the Effelsberg-100 m telescope toward IRC +10216. It covers the frequency range between 17.8 GHz and 26.3 GHz (K-band). In the circumstellar shell of IRC +10216, we find 78 spectral lines, among which 12 remain unidentified. The identified lines are assigned to 18 different molecules and radicals. A total of 23 lines from species known to exist in this envelope are detected for the first time outside the Solar System and there are additional 20 lines first detected in IRC +10216. The potential orgin of "U" lines is also discussed. Assuming local thermodynamic equilibrium (LTE), we then determine rotational temperatures and column densities of 17 detected molecules. Molecular abundances relative to H$_{2}$ are also estimated. A non-LTE analysis of NH$_{3}$ shows that the bulk of its emission arises from the inner envelope with a kinetic temperature of 70$\pm$20 K. Evidence for NH$_{3}$ emitting gas with higher kinetic temperature is also obtained, and potential abundance differences between various $^{13}$C-bearing isotopologues of HC$_{5}$N are evaluated. Overall, the isotopic $^{12}$C/$^{13}$C ratio is estimated to be 49$\pm$9. Finally, a comparison of detected molecules in the $\lambda$ $\sim$1.3 cm range with the dark cloud TMC-1 indicates that silicate-bearing molecules are more predominant in IRC +10216., Comment: 32 pages, 9 figures, Accepted by A&A

We report the first interstellar detection of c-C3D2. The doubly deuterated cyclopropenylidene, a carbene, has been detected toward the starless cores TMC- 1C and L1544 using the IRAM 30m telescope. The J(Ka,Kc) = 3(0,3)-2(1,2), 3(1,3)-2(0,2), and 2(2,1)-1(1,0) transitions of this species have been observed at 3 mm in both sources. The expected 1:2 intensity ratio has been found in the 3(0,3)-2(1,2) and 3(1,3)-2(0,2) lines, belonging to the para and ortho species respectively. We also observed lines of the main species, c-C3H2, the singly deuterated c-C3HD, and the species with one 13C off of the principal axis of the molecule, c-H13CC2H. The lines of c-C3D2 have been observed with high signal to noise ratio, better than 7.5 sigma in TMC-1C and 9 sigma in L1544. The abundance of doubly deuterated cyclopropenylidene with respect to the normal species is found to be (0.4 - 0.8)% in TMC-1C and (1.2 - 2.1)% in L1544. The deuteration of this small hydrocarbon ring is analysed with a comprehensive gas-grain model, the first including doubly deuterated species. The observed abundances of c-C3D2 can be explained solely by gas-phase processes, supporting the idea that c-C3H2 is a good indicator of gas-phase deuteration., Comment: Accepted for publication in ApJ Letters