Context. Observational constraints on dust properties in protoplanetary disks are key to better understanding disk evolution, their dynamics, and the pathway to planet formation, but also surface chemistry, the main driver of chemical complexity. Aims. We continue our exploration of the protoplanetary disk around AB Aur by characterizing its dust properties at different millimeter wavelengths. Methods. We present new ALMA observations at 2.2 mm and VLA observations at 6.8 mm. Together with previous ALMA and NOEMA observations at 0.87 and 1.1 mm, these new observations are used to compute global spectral index profiles as well as spectral index maps to probe the dust properties throughout the disk. On the interpretation side, we present the results of a simple isothermal slab model to help constrain dust properties along the non-axisymmetric ring of continuum emission outside the millimeter cavity. We also present new results of dust radiative transfer calculations based on a disk-planet hydrodynamical simulation to explain how the azimuthal contrast ratio of the ring emission varies with millimeter wavelength. Results. The spectral energy distribution and the radial profiles of the spectral index indicate that the radiation from the compact source towards the center is not dominated by dust thermal emission, but most likely by free-free emission originating in the radio jet; it constitutes 93% of the emission at 6.8 mm, and 37% at 0.87 mm. The protoplanetary disk has a typical spectral index of 2.3, computed using the 0.87, 1.1, and 2.2 mm bands. We estimate a dust disk mass of 8 x 10(-5) M-circle dot which, assuming a mean gas-to-dust ratio of 40, gives a total disk mass of 3.2 x 10(-3) M-circle dot. The azimuthal contrast ratio of the ring outside the millimeter cavity is smaller at 2.2 mm than at 1.1 mm, in agreement with previous findings. The VLA image shows several knots of 5 sigma emission all along the ring, which, with the help of our dust radiative transfer calculations, are consistent with the ring emission being nearly axisymmetric at that wavelength. The decrease in the azimuthal contrast ratio of the ring emission from 0.87 to 6.8 mm can be explained by a dust-losing decaying vortex at the outer edge of a planet gap.

The observational detection of some metastable isomers in the interstellar medium with abundances comparable to those of the most stable isomer, or even when the stable isomer is not detected, highlights the importance of non-equilibrium chemistry. This challenges our understanding of the interstellar chemistry. We present a chemical study of isomers through the sulphur isomer pair HNCS and HSCN, since HSCN has been observed in regions where its stable isomer has not been detected, and the observed HNCS/HSCN ratio seems to significantly vary from cold to warm regions. We have used the Nautilus chemical code to model the formation and destruction paths of HNCS and HSCN in different astrochemical scenarios, and the time evolution of the HNCS/HSCN ratio. We have also analysed the influence of the environmental conditions on their chemical abundances. We present an observational detection of the metastable isomer HSCN in the Class I object B1-a, but not of the stable isomer HNCS, despite HNCS lying 3200 K lower in energy than HSCN. Our results show an HNCS/HSCN ratio sensitive to the gas temperature and the evolutionary time, with the highest values obtained at early stages (t<10^4 yr) and low (Tg<20 K) temperatures. The results suggest a different efficiency of the isomerisation processes depending on the source temperature. The progressive decrease of HNCS/HSCN with gas temperature at early evolutionary times indicates that this ratio may be used as a tracer of cold young objects. This work also demonstrates the key role of grain surface chemistry in the formation of the isomer pair HNCS and HSCN in cold regions, and the importance of the ions H2NCS+ and HNCSH+ in warm/hot regions. Since most of the interstellar regions where HSCN is detected are cold regions, a larger sample including sources characterised by high temperatures are needed to corroborate the theoretical results.

Context. We explore the chemistry of the most abundant C-, O-, S-, and N-bearing species in molecular clouds, in the context of the IRAM 30 m Large Programme Gas phase Elemental abundances in Molecular Clouds (GEMS). Thus far, we have studied the impact of the variations in the temperature, density, cosmic-ray ionisation rate, and incident UV field in a set of abundant molecular species. In addition, the observed molecular abundances might be affected by turbulence which needs to be accounted for in order to have a more accurate description of the chemistry of interstellar filaments. Aims. In this work, we aim to assess the limitations introduced in the observational works when a uniform density is assumed along the line of sight for fitting the observations, developing a very simple numerical model of a turbulent box. We searched for any observational imprints that might provide useful information on the turbulent state of the cloud based on kinematical or chemical tracers. Methods. We performed a magnetohydrodynamical (MHD) simulation in order to reproduce the turbulent steady state of a turbulent box with properties typical of a molecular filament before collapse. We post-processed the results of the MHD simulation with a chemical code to predict molecular abundances, and then post-processed this cube with a radiative transfer code to create synthetic emission maps for a series of rotational transitions observed during the GEMS project. Results. From the kinematical point of view, we find that the relative alignment between the observer and the mean magnetic field direction affect the observed line profiles, obtaining larger line widths for the case when the line of sight is perpendicular to the magnetic field. These differences might be detectable even after convolution with the IRAM 30 m efficiency for a nearby molecular cloud. From the chemical point of view, we find that turbulence produces variations for the predicted abundances, but they are more or less critical depending on the chosen transition and the chemical age. When compared to real observations, the results from the turbulent simulation provides a better fit than when assuming a uniform gas distribution along the line of sight. Conclusions. In the view of our results, we conclude that taking into account turbulence when fitting observations might significantly improve the agreement with model predictions. This is especially important for sulfur bearing species which are very sensitive to the variations of density produced by turbulence at early times (0.1 Myr). The abundance of CO is also quite sensitive to turbulence when considering the evolution beyond a few 0.1 Myr.

Context. 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. Aims. Our goal is to 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. Methods. We used updated collisional rates of HCN, HNC, and their isotopologues in our analysis of the chemistry of TMC 1-C (Taurus) and NGC 1333-C7 (Perseus). 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. Results. The (HCN)-C-13/(HNC)-C-13 ratio is anticorrelated with the deuterium fraction of HCN, thus it can readily serve as a proxy for the temperature. The spectral index (beta similar to 1.34-2.09) shows a tentative anticorrelation with the (HCN)-C-13/(HNC)-C-13 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. Conclusions. 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.

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.

Context. 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 B 335 through observations in the spectral range λ = 7, 3, and 2 mm. Aims. Our goal is to characterise the sulphur chemistry in this isolated protostellar source and compare it with other Class 0 objects to determine the environmental and evolutionary effects on the sulphur chemistry in these young sources. Methods. We have modelled observations and computed column densities assuming local thermodynamic equilibrium and large velocity gradient approximation. We have also used the code Nautilus to study the time evolution of sulphur species, as well as of several sulphur molecular ratios. Results. We have detected 20 sulphur species in B 335 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 B 335 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 B 335. Model results also show the large influence of the cosmic ray ionisation rate and density variations on the abundances of some S species (e.g. SO, SO2, CCS, and CCCS) with differences of up to ~4 orders of magnitude. 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. Conclusions. The comparison between our model and observational results for B 335 reveals an age of 104 < t < 105 yr, which high-lights the particularly early evolutionary stage of this source. B 335 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 B 335. In addition, the theoretical analysis and comparison with observations 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.

Context. Gas phase Elemental abundances in molecular CloudS (GEMS) is an IRAM 30-m 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. Aims. This paper aims to constrain the sulfur elemental abundance in Taurus, Perseus, and Orion A based on the GEMS molecular database. The selected regions are prototypes of low-mass, intermediate-mass, and high-mass star-forming regions, respectively, providing useful templates for the study of interstellar chemistry. Methods. We have carried out an extensive chemical modeling of the fractional abundances of CO, HCO+, HCN, HNC, CS, SO, H2S, OCS, and HCS+ to determine the sulfur depletion toward the 244 positions in the GEMS database. These positions sample visual extinctions from A(V) similar to 3 mag to >50 mag, molecular hydrogen densities ranging from a few x 10(3) cm(-3) to 3 x 10(6) cm(-3), and T-k similar to 10-35 K. We investigate the possible relationship between sulfur depletion and the grain charge distribution in different environments. Results. Most of the positions in Taurus and Perseus are best fitted assuming early-time chemistry, t = 0.1 Myr, zeta(H2) similar to (0.5-1) x 10(-16) s(-1), and [S/H] similar to 1.5 x 10(-6). On the contrary, most of the positions in Orion are fitted with t = 1 Myr and zeta(H2) similar to 10(-17) s(-1). Moreover, similar to 40% of the positions in Orion are best fitted assuming the undepleted sulfur abundance, [S/H] similar to 1.5 x 10(-5). We find a tentative trend of sulfur depletion increasing with density. Conclusions. 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 similar to 20 is required to explain those observed in Taurus and Perseus. We propose that differences in the grain charge distribution might explain these variations. Grains become negatively charged at a visual extinction of A(V) similar to 3.5 mag in Taurus and Perseus. At this low visual extinction, the S+ abundance is high, X(S+) > 10(-6), and the electrostatic attraction between S+ and negatively charged grains could contribute to enhance sulfur depletion. In Orion, the net charge of grains remains approximately zero until higher visual extinctions (A(V) similar to 5.5 mag), where the abundance of S+ is already low because of the higher densities, thus reducing sulfur accretion. The shocks associated with past and ongoing star formation could also contribute to enhance [S/H].

Context. H 2 S is predicted to form by hydrogenation of atomic sulphur on grains and is thought to be the main sulphur reservoir in interstellar ice, being therefore a key molecule to understanding sulphur chemistry in the star formation process and to solving the missing sulphur problem in molecular clouds and star-forming regions. The study of the H 2 S deuterium fraction can be used to constrain its molecule formation pathways. Aims. The aim of this work is to investigate for the first time the deuteration of H 2 S in a large sample of starless cores. Methods. We used observations of the GEMS IRAM 30 m Large Program and complementary IRAM 30 m telescope observations. We considered a sample of 19 starless cores located in the Taurus, Perseus, and Orion molecular clouds, detecting HDS in ten of these starless cores, and D 2 S in five. The single and double H 2 S deuterium fractions were analysed with regard to their relation with the cloud physical parameters, comparisons with values obtained for other interstellar sources, and comparisons with deuterium fractions in early-stage star-forming sources of abundant molecules: c-C 3 H 2 , H 2 CS, H 2 O, H 2 CO, and CH 3 OH. Results. We obtain a range of X(HDS)/X(H 2 S) ~ 0.025–0.2 in the starless cores with HDS detections. The five starless cores with D 2 S detections show values of X(D 2 S)/X(HDS) ~ 0.05–0.3. H 2 S single deuteration shows an inverse relation with the cloud kinetic temperature, but no trend is found with molecular hydrogen density or visual extinction. H 2 S deuteration values in starless cores are similar to those observed in Class 0, although this may be a consequence of an observational bias due to the limited spatial resolution. Comparison with c-C 3 H 2 , H 2 CS, H 2 O, H 2 CO, and CH 3 OH in other interstellar sources reveals a general trend of decreasing deuteration with increasing temperature, with lower values for Class I and massive star-forming sources. In starless cores and Class 0 objects, H 2 CS and H 2 CO present higher deuteration fractions than c-C 3 H 2 , H 2 S, H 2 O, and CH 3 OH. H 2 O shows single and double deuteration values one order of magnitude lower than those of H 2 S and CH 3 OH. Conclusions. Differences between c-C 3 H 2 , H 2 CS and H 2 CO deuterium fractions and those of H 2 S, H 2 O, and CH 3 OH are related to deuteration processes produced in gas or solid phases, respectively. We interpret the differences between H 2 S and CH 3 OH deuterations and that of H 2 O as a consequence of differences in the formation routes in the solid phase, which can particularly be explained in terms of the different occurrence of the D-H and H-D substitution reactions in the ice, together with the chemical desorption processes. Further interferometric observations and laboratory experiments are needed to understand the deuteration processes.

Context. 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. Aims. Our goal is to 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. Methods. We used updated collisional rates of HCN, HNC, and their isotopologues in our analysis of the chemistry of TMC 1-C (Taurus) and NGC 1333-C7 (Perseus). 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 µm allowed us to compute the emissivity spectral index and look for grain growth as an evolutionary tracer. Results. 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 ( β ~ 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. Conclusions. 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.

Context. Deuteration is a crucial tool for understanding 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. Aims. We aim to study 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. Methods. Here, we present single-dish observations of H2CS, HDCS and D2CS with the IRAM 30 m telescope. We analysed their column densities and distributions and compared these observations with gas–grain chemical models. The deuteration maps of H2CS in L1544 were compared with the deuteration maps of methanol, H2CO, N2H+, and HCO+ towards the same source. Furthermore, we compared the single and double deuteration of H2CS towards the dust peak of L1544 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. Results. The maximum deuterium fractionation for the first deuteration of H2CS is N(HDCS)/N(H2CS) ~ 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 ~ 100% (with X = O or S). Conclusions. 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, 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.

Context. AB Aur is a Herbig Ae star that hosts a prototypical transition disk. The disk shows a plethora of features connected with planet formation mechanisms, such as spiral arms, dust cavities, and dust traps. Understanding the physical and chemical characteristics of these features is crucial to advancing our knowledge of the planet formation processes. Aims. We aim to characterize the gaseous disk around the Herbig Ae star AB Aur. A complete spectroscopic study was performed using NOEMA to determine the physical and chemical conditions with high spatial resolution. Methods. We present new NOrthern Extended Millimeter Array (NOEMA) interferometric observations of the continuum and 12 CO, 13 CO, C 18 O, H 2 CO, and SO lines obtained at high resolution. We used the integrated intensity maps and stacked spectra to derive reliable estimates of the disk temperature. By combining our 13 CO and C 18 O observations, we computed the gas-to-dust ratio along the disk. We also derived column density maps for the different species and used them to compute abundance maps. The results of our observations were compared with a set of Nautilus astrochemical models to obtain insight into the disk properties. Results. We detected continuum emission in a ring that extends from 0.6′′ to ~2.0′′, peaking at 0.97′′ and with a strong azimuthal asymmetry. The molecules observed show different spatial distributions, and the peaks of the distributions are not correlated with the binding energy. Using H 2 CO and SO lines, we derived a mean disk temperature of 39 K. We derived a gas-to-dust ratio that ranges from 10 to 40 along the disk. Abundance with respect to 13 CO for SO (~2 × 10 −4 ) is almost one order of magnitude greater than the value derived for H 2 CO (1.6 × 10 −5 ). The comparison with Nautilus models favors a disk with a low gas-to-dust ratio (40) and prominent sulfur depletion. Conclusions. From a very complete spectroscopic study of the prototypical disk around AB Aur, we derived, for the first time, the gas temperature and the gas-to-dust ratio along the disk, providing information that is essential to constraining hydrodynamical simulations. Moreover, we explored the gas chemistry and, in particular, the sulfur depletion. The derived sulfur depletion is dependent on the assumed C/O ratio. Our data are better explained with C/O ~ 0.7 and S/H = 8 × 10 −8 .

Gas phase Elemental abundances in Molecular CloudS (GEMS) is an IRAM 30 m Large Program designed to provide estimates of the S, C, N, and O depletions and gas ionization degree, X(e−), in a selected set of star-forming filaments of Taurus, Perseus, and Orion. Our immediate goal is to build up a complete and large 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 theAV~3 to ~100 mag,n(H2) ~ a few 103to 106cm−3, andTk~10 to ~30 K ranges in these clouds, and avoiding protostars, HII regions, and bipolar outflows. A statistical analysis is carried out in order to identify general trends between different species and with physical parameters. Relations between molecules reveal strong linear correlations which define three different families of species: (1)13CO and C18O isotopologs; (2) H13CO+, HC18O+, H13CN, and HNC; and (3) the S-bearing molecules. The abundances of the CO isotopologs increase with the gas kinetic temperature untilTK~ 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 ± 0.2. The abundances of S-bearing species also decrease with molecular hydrogen density at a rate of (S-bearing/H)gas∝n(H2)−0.6 ± 0.1. 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 the13CO/C18O, HCO+/H13CO+, and H13CO+/H13CN abundance ratios as chemical diagnostics of star formation in external galaxies.

Context. Carbon monosulphide (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. However, chemical models fail to account for the observed CS abundances when assuming the cosmic value for the elemental abundance of sulfur.Aims. 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. Our goal is to calculate the CS+O reaction rate at temperatures <150 K which are prevailing in the interstellar medium.Methods. We performed ab initio calculations to obtain the three lowest potential energy surfaces (PES) of the CS+O system. These PESs are used to study the reaction dynamics, using several methods (classical, quantum, and semiclassical) to eventually calculate the CS + O thermal reaction rates. In order to check the accuracy of our calculations, we compare the results of our theoretical calculations for T ~ 150−400 K with those obtained in the laboratory.Results. 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, below 10−15 cm3 s−1, which is consistent with the extrapolation of experimental data using the Arrhenius expression.Conclusions. We use the updated chemical network to model the sulfur chemistry in Taurus Molecular Cloud 1 (TMC 1) based on molecular abundances determined from Gas phase Elemental abundances in Molecular CloudS (GEMS) project observations. In our model, we take into account the expected decrease of the cosmic ray ionization rate, ζH2, along the cloud. The abundance of CS is still overestimated when assuming the cosmic value for the sulfur abundance.

Context. Carbon monosulphide (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. However, chemical models fail to account for the observed CS abundances when assuming the cosmic value for the elemental abundance of sulfur. Aims. 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. Our goal is to calculate the CS+O reaction rate at temperatures <150 K which are prevailing in the interstellar medium. Methods. We performed ab initio calculations to obtain the three lowest potential energy surfaces (PES) of the CS+O system. These PESs are used to study the reaction dynamics, using several methods (classical, quantum, and semiclassical) to eventually calculate the CS + O thermal reaction rates. In order to check the accuracy of our calculations, we compare the results of our theoretical calculations for T similar to 150-400 K with those obtained in the laboratory. Results. 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, below 10(-15) cm(3) s(-1), which is consistent with the extrapolation of experimental data using the Arrhenius expression. Conclusions. We use the updated chemical network to model the sulfur chemistry in Taurus Molecular Cloud 1 (TMC 1) based on molecular abundances determined from Gas phase Elemental abundances in Molecular CloudS (GEMS) project observations. In our model, we take into account the expected decrease of the cosmic ray ionization rate, zeta(H2), along the cloud. The abundance of CS is still overestimated when assuming the cosmic value for the sulfur abundance.

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.

Studies on the effects of ultraviolet (UV) photons impinging on dust grains have revealed their importance for the interstellar chemistry evolution. While grain surface reactions generally produce simple molecular ice mantles, UV irradiation leads to the formation of more complex species, enhancing thus the interstellar gas phase. In fact, species as complex as sugars and amino acids have been obtained in laboratory experiments by irradiating ice analogs with UV photons. This demonstrates the key role of the interstellar grain photochemistry in the formation of the building blocks of life. This article aims to review the main advances carried out on interstellar grain photochemistry over the last decades, as well as the different approaches and techniques used.

Spectroscopic studies of ices in nearby star-forming regions indicate that ice mantles form on dust grains in two distinct steps, starting with polar ice formation (H2O rich) and switching to apolar ice (CO rich). We test how well the picture applies to more diffuse and quiescent clouds where the formation of the first layers of ice mantles can be witnessed. Medium-resolution near-infrared spectra are obtained toward background field stars behind the Pipe Nebula. The water ice absorption is positively detected at 3.0 micron in seven lines of sight out of 21 sources for which observed spectra are successfully reduced. The peak optical depth of the water ice is significantly lower than those in Taurus with the same visual extinction. The source with the highest water-ice optical depth shows CO ice absorption at 4.7 micron as well. The fractional abundance of CO ice with respect to water ice is 16+7-6 %, and about half as much as the values typically seen in low-mass star-forming regions. A small fractional abundance of CO ice is consistent with some of the existing simulations. Observations of CO2 ice in the early diffuse phase of a cloud play a decisive role in understanding the switching mechanism between polar and apolar ice formation.

The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 117 chemical reactions occurring on grain surfaces covering different processes, such as adsorption, thermal desorption, chemical desorption, two-body reactions, photo processes, and cosmic-ray processes on dust grains. We obtain abundances for different gas and solid species as a function of visual extinction, depending on the density and radiation field. We also analyse the rates of the formation of CO2 and H2O ices in different environments. In addition, we study how chemistry is affected by the presence/absence of ice mantles (bare dust or icy dust) and the impact of considering different desorption probabilities. The type of substrate (bare dust or icy dust) and the probability of desorption can significantly alter the chemistry occurring on grain surfaces, leading to differences of several orders of magnitude in the abundances of gas-phase species, such as CO, H2CO, and CH3OH. The type of substrate, together with the density and intensity of the radiation field, also determine the threshold extinction to form ices of CO2 and H2O. We also conclude that H2CO and CH3OH are mainly released into the gas phase of low, far-ultraviolet illuminated PDRs through chemical desorption upon two-body surface reactions, rather than through photodesorption.