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Context. 1-propanol (CH3CH2CH2OH) is a three carbon-bearing representative of the primary linear alcohols that may have its origin in the cold dark cores in interstellar space. To test this, we investigated in the laboratory whether 1-propanol ice can be formed along pathways possibly relevant to the prestellar core phase. Aims. We aim to show in a two-step approach that 1-propanol can be formed through reaction steps that are expected to take place during the heavy CO freeze-out stage by adding C2H2 into the CO + H hydrogenation network via the formation of propanal (CH3CH2CHO) as an intermediate and its subsequent hydrogenation. Methods. Temperature programmed desorption-quadrupole mass spectrometry (TPD-QMS) was used to identify the newly formed propanal and 1-propanol. Reflection absorption infrared spectroscopy (RAIRS) was used as a complementary diagnostic tool. The mechanisms that can contribute to the formation of solid-state propanal and 1-propanol, as well as other organic compounds, during the heavy CO freeze-out stage are constrained by both laboratory experiments and theoretical calculations. Results. Here it is shown that recombination of HCO radicals formed upon CO hydrogenation with radicals formed via C2H2 processing – H2CCH and H3CCH2 – offers possible reaction pathways to solid-state propanal and 1-propanol formation. This extends the already important role of the CO hydrogenation chain to the formation of larger complex organic molecules. The results are compared with ALMA observations. The resulting 1-propanol:propanal ratio concludes an upper limit of <0.35−0.55, which is complemented by computationally derived activation barriers in addition to the experimental results. [ABSTRACT FROM AUTHOR]

The emergence of life on Earth may have its origin in organic molecules formed in the interstellar medium. Molecules with amide and isocyanate groups resemble structures found in peptides and nucleobases and are necessary for their formation. Their formation is expected to take place in the solid state, on icy dust grains, and is studied here by far-UV irradiating a CH4:HNCO mixture at 20 K in the laboratory. Reaction products are detected by means of infrared spectroscopy and temperature programmed desorption - mass spectrometry. Various simple amides and isocyanates are formed, showing the importance of ice chemistry for their interstellar formation. Constrained by experimental conditions, a reaction network is derived, showing possible formation pathways of these species under interstellar conditions. [ABSTRACT FROM AUTHOR]

Interstellar complex organic molecules are thought to be the building blocks of more complex prebiotic compounds. In particular, formamide (or methanimide, NH2CHO), is presented as a multifunctional prebiotic precursor, the starting point of both pre-genetic and pre-metabolic species. NH2CHO is widely observed in different astrophysical media as well as in comets that may have had a crucial role in the delivery of exogenous material to Earth. In star-forming regions, gas phase synthesis of formamide is possible, even if it is still debated. In this paper we present laboratory experiments demonstrating formamide formation in interstellar ice analogues at astronomically relevant temperatures via simultaneous hydrogenation of NO and H2CO, two abundant molecules in star-forming regions. Inclusion of the experimental results in an astrochemical gas-grain model confirms the importance of the investigated solid-state reaction channel leading a high yield of formamide in dark interstellar clouds, and adds a valuable perspective about the way this refractory molecule may have been part of the prebiotic molecular building blocks delivered to the young Earth. [ABSTRACT FROM AUTHOR]

We present the first census of the interstellar Complex Organic Molecules (iCOMs) in the low-mass Class I protostar SVS13-A, obtained by analysing data from the IRAM-30 m Large Project ASAI (Astrochemical Surveys At IRAM). They consist of a high-sensitivity unbiased spectral survey at the 1mm, 2mm, and 3mm IRAM bands. We detected five iCOMs: acetaldehyde (CH3CHO), methyl formate (HCOOCH3), dimethyl ether (CH3OCH3), ethanol (CH3CH2OH), and formamide (NH2CHO). In addition, we searched for other iCOMs and ketene (H2CCO), formic acid (HCOOH) and methoxy (CH3O), whose only ketene was detected. The numerous detected lines, from 5 to 37 depending on the species, cover a large upper level energy range, between 15 and 254 K. This allowed us to carry out a rotational diagram analysis and derive rotational temperatures between 35 and 110 K, and column densities between 3 × 1015 and 1 × 1017 cm−2 on the 0.3 arcsec size previously determined by interferometric observations of glycolaldehyde. These new observations clearly demonstrate the presence of a rich chemistry in the hot corino towards SVS13-A. The measured iCOMs abundances were compared to other Class 0 and I hot corinos, as well as comets, previously published in the literature. We find evidence that (i) SVS13-A is as chemically rich as younger Class 0 protostars, and (ii) the iCOMs relative abundances do not substantially evolve during the protostellar phase. [ABSTRACT FROM AUTHOR]

Context. One of the important questions of astrochemistry is how complex organic molecules, including potential prebiotic species, are formed in the envelopes around embedded protostars. The abundances of minor isotopologues of a molecule, in particular the D- and 13C-bearing variants, are sensitive to the densities, temperatures and timescales characteristic of the environment in which they form, and can therefore provide important constraints on the formation routes and conditions of individual species. Aims. The aim of this paper is to systematically survey the deuteration and the 13C content of a variety of oxygen-bearing complex organic molecules on solar system scales toward the "B component" of the protostellar binary IRAS16293–2422. Methods. We have used the data from an unbiased molecular line survey of the protostellar binary IRAS16293−2422 between 329 and 363 GHz from the Atacama Large Millimeter/submillimeter Array (ALMA). The data probe scales of 60 AU (diameter) where most of the organic molecules are expected to have sublimated off dust grains and be present in the gas phase. The deuterated and 13C isotopic species of ketene, acetaldehyde and formic acid, as well as deuterated ethanol, are detected unambiguously for the first time in the interstellar medium. These species are analysed together with the 13C isotopic species of ethanol, dimethyl ether and methyl formate along with mono-deuterated methanol, dimethyl ether and methyl formate. Results. The complex organic molecules can be divided into two groups with one group, the simpler species, showing a D/H ratio of ≈2% and the other, the more complex species, D/H ratios of 4–8%. This division may reflect the formation time of each species in the ices before or during warm-up/infall of material through the protostellar envelope. No significant differences are seen in the deuteration of different functional groups for individual species, possibly a result of the short timescale for infall through the innermost warm regions where exchange reactions between different species may be taking place. The species show differences in excitation temperatures between 125 and 300 K. This likely reflects the binding energies of the individual species, in good agreement with what has previously been found for high-mass sources. For dimethyl ether, the 12C/13C ratio is found to be lower by up to a factor of 2 compared to typical ISM values similar to what has previously been inferred for glycolaldehyde. Tentative identifications suggest that the same may apply for 13C isotopologues of methyl formate and ethanol. If confirmed, this may be a clue to their formation at the late prestellar or early protostellar phases with an enhancement of the available 13C relative to 12C related to small differences in binding energies for CO isotopologues or the impact of FUV irradiation by the central protostar. Conclusions. The results point to the importance of ice surface chemistry for the formation of these complex organic molecules at different stages in the evolution of embedded protostars and demonstrate the use of accurate isotope measurements for understanding the history of individual species. [ABSTRACT FROM AUTHOR]

Molecules with an amide functional group resemble peptide bonds, the molecular bridges that connect amino acids, and may thus be relevant in processes that lead to the formation of life. In this study, the solid state formation of some of the smallest amides is investigated in the laboratory. To this end, CH4:HNCO ice mixtures at 20 K are irradiated with far-UV photons, where the radiation is used as a tool to produce the radicals required for the formation of the amides. Products are identified and investigated with infrared spectroscopy and temperature-programmed desorption mass spectrometry. The laboratory data show that NH2CHO, CH3NCO, NH2C(O)NH2, CH3C(O)NH2, and CH3NH2 can simultaneously be formed. The NH2CO radical is found to be key in the formation of larger amides. In parallel, ALMA observations towards the low-mass protostar IRAS 16293–2422B are analysed in search of CH3NHCHO (N-methylformamide) and CH3C(O)NH2 (acetamide). CH3C(O)NH2 is tentatively detected towards IRAS 16293–2422B at an abundance comparable with those found towards high-mass sources. The combined laboratory and observational data indicate that NH2CHO and CH3C(O)NH2 are chemically linked and form in the ice mantles of interstellar dust grains. A solid-state reaction network for the formation of these amides is proposed. [ABSTRACT FROM AUTHOR]

We present the results of formaldehyde and methanol deuteration measurements towards the Class I low-mass protostar SVS13-A in the framework of the IRAM 30-m ASAI (Astrochemical Surveys at IRAM) project. We detected emission lines of formaldehyde, methanol and their deuterated forms (HDCO, D2CO, CHD2OH, CH3OD) with Eup up to 276 K. The formaldehyde analysis indicates Tkin ~ 15-30 K, ... ≥ 106 cm-3 and a size of about 1200 au suggesting an origin in the protostellar envelope. For methanol, we find two components: (i) a high temperature (Tkin ~ 80 K) and very dense (>108 cm-3) gas from a hot corino (radius ≃ 35 au), and (ii) a colder (Tkin ≤ 70 K) and more extended (radius ≃ 350 au) region. The deuterium fractionation is 9 x 10-2 for HDCO, 4 x 10-3 for D2CO and 2-7 x 10-3 for CH2DOH, up to two orders of magnitude lower than the values measured in Class 0 sources. We also derive formaldehyde deuteration in the outflow: 4 x 10-3, in agreement with what found in the L1157-B1 protostellar shock. Finally, we estimate [CH2DOH]/[CH3OD] ≃ 2. The decrease of deuteration in the Class I source SVS13-A with respect to Class 0 sources can be explained by gas-phase processes. Alternatively, a lower deuteration could be the effect of a gradual collapse of less deuterated external shells of the protostellar envelope. The present measurements fill in the gap between pre-stellar cores and protoplanetary discs in the context of organic deuteration measurements. [ABSTRACT FROM AUTHOR]

Context. Astrochemical models commonly used to study the deuterium chemistry in starless cores consider a two-phase approach in which the ice on the dust grains is assumed to be entirely reactive. Recent experimental studies suggest that cold interstellar ices are mostly inert, and a multilayer model distinguishing the chemical processes at the surface and in the ice bulk would be more appropriate. Aims. We investigate whether the multilayer model can be as successful as the bulk model in reproducing the observed abundances of various deuterated gas-phase species toward starless cores. Methods. We calculated abundances for various deuterated species as functions of time using a pseudo-time-dependent chemical model adopting fixed physical conditions. We also estimated abundance gradients in starless cores by adopting a modified Bonnor-Ebert sphere as a core model. In the multilayer ice scenario, we consider desorption from one or several monolayers on the surface. Results. We find that the multilayer model predicts abundances of DCO+ and N2D+ that are about an order of magnitude lower than observed; the difference is caused by the trapping of CO and N2 within the grain mantle. As a result of the mantle trapping, deuteration efficiency in the gas phase increases and we find stronger deuterium fractionation in ammonia than has been observed. Another distinguishing feature of the multilayer model is that D3+ becomes the main deuterated ion at high density. The bulk ice model is generally easily reconciled with observations. Conclusions. Our results underline that more theoretical and experimental work is needed to understand the composition and morphology of interstellar ices, and the desorption processes that can act on them. With the current constraints, the bulk ice model appears to reproduce the observations more accurately than the multilayer ice model. According to our results, the abundance ratio of H2D+ to N2D+ is higher than 100 in the multilayer model, while only a few ?10 in the bulk model, and so observations of this ratio could provide information on the ice morphology in starless cores. Observations of the abundance of D3+ compared to H2D+ and D2H+, although challenging, would provide additional constraints for the models. [ABSTRACT FROM AUTHOR]

Context. The measure of the water deuterium fractionation is a relevant tool for understanding mechanisms of water formation and evolution from the prestellar phase to the formation of planets and comets. Aims. The aim of this paper is to study deuterated water in the solar-type protostars NGC 1333 IRAS 4A and IRAS 4B, to compare their HDO abundance distributions with other star-forming regions, and to constrain their HDO/H2O abundance ratios. Methods. Using the Herschel/HIFI instrument as well as ground-based telescopes, we observed several HDO lines covering a large excitation range (Eup=k = 22-168 K) towards these protostars and an outflow position. Non-local thermal equilibrium radiative transfer codes were then used to determine the HDO abundance profiles in these sources. Results. The HDO fundamental line profiles show a very broad component, tracing the molecular outflows, in addition to a narrower emission component and a narrow absorbing component. In the protostellar envelope of NGC 1333 IRAS 4A, the HDO inner (T ⩾ 100 K) and outer (T < 100 K) abundances with respect to H2 are estimated with a 3σ uncertainty at 7.5+3.5 -3.0x 10-9 and 1.2+0.4 -0.4 x 10-11, respectively, whereas in NGC 1333 IRAS 4B they are 1+1.8 -0.9 × 10-8 and 1.2+0.6 -0.4 × 10-10, respectively. Similarly to the low-mass protostar IRAS 16293-2422, an absorbing outer layer with an enhanced abundance of deuterated water is required to reproduce the absorbing components seen in the fundamental lines at 465 and 894 GHz in both sources. This water-rich layer is probably extended enough to encompass the two sources, as well as parts of the outflows. In the outflows emanating from NGC 1333 IRAS 4A, the HDO column density is estimated at about (2-4) × 1013 cm-2, leading to an abundance of about (0.7-1.9) × 10-9. An HDO/H2O ratio between 7 × 10-4 and 9 × 10-2 is also derived in the outflows. In the warm inner regions of these two sources, we estimate the HDO/H2O ratios at about 1 × 10-4 -4 × 10-3. This ratio seems higher (a few %) in the cold envelope of IRAS 4A, whose possible origin is discussed in relation to formation processes of HDO and H2O. Conclusions. In low-mass protostars, the HDO outer abundances range in a small interval, between ~10-11 and a few 10-10. No clear trends are found between the HDO abundance and various source parameters (Lbol, Lsmm, Lsmm/Lbol, Tbol, L0.6 bol/Menv). A tentative correlation is observed, however, between the ratio of the inner and outer abundances with the submillimeter luminosity. [ABSTRACT FROM AUTHOR]

Context. Intermediate-mass stars are an important ingredient of our Galaxy and a key to understanding how high- and low-mass stars form in clusters. One of the closest known young intermediate-mass protoclusters is OMC-2 FIR 4, which is located at a distance of 420 pc in Orion. This region is one of the few where the complete 500-2000 GHz spectrum has been observed with the heterodyne spectrometer HIFI on board the Herschel satellite, and unbiased spectral surveys at 0.8, 1, 2, and 3 mm have been obtained with the JCMT and IRAM 30-m telescopes. Aims. We aim to disentangle the core multiplicity, to investigate the morphology of this region in order to study the formation of a low- and intermediate-mass protostar cluster, and to aid in interpretation of the single-dish line profiles already in our hands. Methods. We used the IRAM Plateau de Bure Interferometer to image OMC-2 FIR 4 in the 2-mm continuum emission, as well as in DCO+(2-1), DCN(2-1), C34S(3-2), and several CH3OH lines. In addition, we analysed observations of the NH3(1, 1) and (2, 2) inversion transitions that used the Very Large Array of the NRAO. The resulting maps have an angular resolution that allows us to resolve structures of 5″ , which is equivalent to ∼2000 AU. Results. Our observations reveal three spatially resolved sources within OMC-2 FIR 4, of one or several solar masses each, with hints of further unresolved substructure within them. Two of these sources have elongated shapes and are associated with dust continuum emission peaks, thus likely containing at least one molecular core each. One of them also displays radio continuum emission, which may be attributed to a young B3-B4 star that dominates the overall luminosity output of the region. The third identified source displays a DCO+(2-1) emission peak and weak dust continuum emission. Its higher abundance of DCO+ relative to the other two regions suggests a lower temperature, hence its possible association with either a younger low-mass protostar or a starless core. It may alternatively be part of the colder envelope of OMC-2 FIR 4. Conclusions. Our interferometric observations show the complexity of the intermediate-mass protocluster OMC-2 FIR 4, where multiple cores, chemical differentiation, and an ionised region all coexist within an area of only 10 000 AU. [ABSTRACT FROM AUTHOR]

Context. Millimetric observations have measured high degrees of molecular deuteration in several species seen around low-mass protostars. The Herschel Space Telescope, launched in 2009, is now providing new measures of the deuterium fractionation of water, the main constituent of interstellar ices. Aims. We aim at theoretically studying the formation and the deuteration of water, which is believed to be formed on interstellar grain surfaces in molecular clouds. Methods. We used our gas-grain astrochemical model GRAINOBLE, which considers the multilayer formation of interstellar ices. We varied several input parameters to study their impact on water deuteration. We included the treatment of ortho- and para-states of key species, including H2, which affects the deuterium fractionation of all molecules. The model also includes relevant laboratory and theoretical works on the water formation and deuteration on grain surfaces. In particular, we computed the transmission probabilities of surface reactions using the Eckart model, and we considered ice photodissociation following molecular dynamics simulations. Results. The use of amultilayer approach allowed us to study the influence of various parameters on the abundance and the deuteration of water. Deuteration of water is found to be very sensitive to the ortho-to-para ratio of H2 and to the total density, but it also depends on the gas/grain temperatures and the visual extinction of the cloud. Since the deuteration is very sensitive to the physical conditions, the comparison with sub-millimetric observation towards the low-mass protostar IRAS 16293 allows us to suggest that water ice is formed together with CO2 in molecular clouds with limited density, whilst formaldehyde and methanol are mainly formed in a later phase, where the condensation becomes denser and colder. [ABSTRACT FROM AUTHOR]

Context. Complex organic molecules (COMs) have long been detected in the interstellar medium, especially in hot cores and in the hot corinos of low-mass protostars. Their formation routes however remain uncertain. Both warm gas-phase reactions and warm grain-surface reactions have been invoked to account for their presence in low-mass protostars. In this latter scheme, COMs result from radical-radical reactions on the grains as radicals become mobile when the nascent protostar warms up its surroundings and the resulting molecules are subsequently desorbed into the gas phase at higher temperatures. Aims. Prestellar cores are the direct precursors of low-mass protostars and offer a unique opportunity to study the formation of COMs before the warm-up phase. Their very low temperatures (≤10K) and the absence of any heating source or outflow exclude any efficient warm gas phase or warm dust chemistry, so that the presence of COMs in prestellar cores would have to originate from non-thermal chemical processes. Methods. We used the IRAM 30m telescope to look for four O-bearing COMs (acetaldehyde CH3CHO, dimethyl ether CH3OCH3, methyl formate CH3OCHO, and ketene CH2CO) in the prestellar core L1689B. Results. We report the unambiguous detection of all four molecules in the cold gas phase of L1689B. These detections support the role played by non-thermal (possibly photolytic) processes in COM formation and desorption, though the presence of dimethyl ether is so far unexplained by current grain formation scenarios. The data show univocally that COM synthesis has already started at the prestellar stage and suggests at least part of the COMs detected in hot corinos have a prestellar origin. [ABSTRACT FROM AUTHOR]

Context. Mantles of iced water mixed with carbon monoxyde, formaldehyde, and methanol are formed during the so-called prestellar core phase. In addition, radicals are also thought to be formed on the grain surfaces, and to react to form complex organic molecules later on, during the so-called warm-up phase of the protostellar evolution. Aims. We aim to study the formation of the grain mantles during the prestellar core phase and the abundance of formaldehyde, methanol, and radicals trapped in them. Methods. We have developed a macrosopic statistic multilayer model that follows the formation of grain mantles with time and that includes two effects that may increase the number of radicals trapped in the mantles: i) during the mantle formation, only the surface layer is chemically active and not the entire bulk; and ii) the porous structure of grains allows the trapping reactive particles. The model considers a network of H, O, and CO forming neutral species such as water, CO, formaldehyde, and methanol, plus several radicals. We ran a large grid of models to study the impact of the mantle multilayer nature and grain porous structure. In addition, we explored how the uncertainty of other key parameters influences the mantle composition. Results. Our model predicts relatively high abundances of radicals, especially of HCO and CH3O (10-9-10-7). In addition, the multilayer approach enables us to follow the chemical differentiation within the grain mantle, showing that the mantles are far from being uniform. For example, methanol is mostly present in the outer layers of the mantles, whereas CO and other reactive species are trapped in the inner layers. The overall mantle composition depends on the density and age of the prestellar core as well as on some microscopic parameters, such as the diffusion energy and the hydrogenation reactions activation energy. Comparison with observations allows us to constrain the value of the last two parameters (0.5-0.65 and 1500 K, respectively) and provide some indications on the physical conditions during the formation of the ices [ABSTRACT FROM AUTHOR]

We utilize a chemical equilibrium code in order to study the condensation process which occurs in protoplanetary discs during the formation of the first solids. The model specifically focuses on the thermodynamic behaviour on the solid species assuming the regular solution model. For each solution, we establish the relationship between the activity of the species, the composition and the temperature using experimental data from the literature. We then apply the Gibbs free energy minimization method and study the resulting condensation sequence for a range of temperatures and pressures within a protoplanetary disc. Our results using the regular solution model show that grains condense over a large temperature range and therefore throughout a large portion of the disc. In the high-temperature region ( T≥ 1400 K) hibonite and gehlenite dominate, and we find that the formation of corundum is sensitive to the pressure. The mid-temperature region is dominated by Fe(s) and silicates such as MgSiO and MgSiO. The chemistry of forsterite and that of enstatite are strictly related, and our simulations show a sequence of forsterite-enstatite-forsterite with decreasing temperature and the abundance of the first high-temperature peak of forsterite is also pressure sensitive. In the low-temperature regions ( T≤ 600 K), a range of iron compounds (FeS, FeSiO, FeAlO) form. We find that all the condensation sequences move towards lower temperature as the pressure decreases. We also run simulations using the ideal solution model and see clear differences in the resulting condensation sequences with changing solution model. In particular, we find that the turning point in which forsterite replaces enstatite in the low-temperature region is sensitive to the solution model. In this same temperature region, fayalite is the most stable compound for the regular solution, while magnetite replaces fayalite in the ideal solution model at the lowest values of temperature. Our results show that the ideal solution model is often a poor approximation to experimental data at most temperatures important in protoplanetary discs. We find some important differences in the resulting condensation sequences when using the regular solution model and suggest that this model should provide a more realistic condensation sequence. [ABSTRACT FROM AUTHOR]

IRAS 04368+2557 is a solar-type (low-mass) protostar embedded in a protostellar core (L1527) in the Taurus molecular cloud, which is only 140 parsecs away from Earth, making it the closest large star-forming region. The protostellar envelope has a flattened shape with a diameter of a thousand astronomical units (1 AU is the distance from Earth to the Sun), and is infalling and rotating. It also has a protostellar disk with a radius of 90 AU (ref. 6), from which a planetary system is expected to form. The interstellar gas, mainly consisting of hydrogen molecules, undergoes a change in density of about three orders of magnitude as it collapses from the envelope into the disk, while being heated from 10 kelvin to over 100 kelvin in the mid-plane, but it has hitherto not been possible to explore changes in chemical composition associated with this collapse. Here we report that the unsaturated hydrocarbon molecule cyclic-C3H2 resides in the infalling rotating envelope, whereas sulphur monoxide (SO) is enhanced in the transition zone at the radius of the centrifugal barrier (100 ± 20 AU), which is the radius at which the kinetic energy of the infalling gas is converted to rotational energy. Such a drastic change in chemistry at the centrifugal barrier was not anticipated, but is probably caused by the discontinuous infalling motion at the centrifugal barrier and local heating processes there.