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Aims. The ability of bulk ices (H2O, CO2) to trap volatiles has been well studied in any experimental sense, but largely ignored in protoplanetary disk and planet formation models as well as the interpretation of their observations. We demonstrate the influence of volatile trapping on C/O ratios in planet-forming environments. Methods. We created a simple model of CO, CO2, and H2O snowlines in protoplanetary disks and calculated the C/O ratio at different radii and temperatures. We included a trapping factor, which partially inhibits the release of volatiles (CO, CO2) at their snowline and releases them instead, together with the bulk ice species (H2O, CO2). Our aim has been to assess its influence of trapping solid-state and gas phase C/O ratios throughout planet-forming environments. Results. Volatile trapping significantly affects C/O ratios in protoplanetary disks. Variations in the ratio are reduced and become more homogeneous throughout the disk when compared to models that do not include volatile trapping. Trapping reduces the proportion of volatiles in the gas and, as such, reduces the available carbon- and oxygen-bearing molecules for gaseous accretion to planetary atmospheres. Volatile trapping is expected to also affect the elemental hydrogen and nitrogen budgets. Conclusions. Volatile trapping is an overlooked, but important effect to consider when assessing the C/O ratios in protoplanetary disks and exoplanet atmospheres. Due to volatile trapping, exoplanets with stellar C/O have the possibility to be formed within the CO and CO2 snowline. [ABSTRACT FROM AUTHOR]

Context. Interstellar surface chemistry is a complex process that occurs in icy layers that have accumulated onto grains of different sizes. The efficiency of the surface processes often depends on the immediate environment of the adsorbed molecules. Aims. We investigated how gas-grain chemistry changes when the surface molecule binding energy is modified, depending on the properties of the surface. Methods. In a gas-grain astrochemical model, molecular binding energy gradually changes for three different environments –(1) the bare grain surface, (2) polar water-dominated ices, and (3) weakly polar carbon monoxide-dominated ices. In addition to diffusion, evaporation, and chemical desorption, photodesorption was also made binding energy-dependent, in line with experimental results. These phenomena occur in a collapsing prestellar core model that considers five grain sizes with ices arranged into four layers. Results. Variable desorption energy moderately affects gas-grain chemistry. Bare-grain effects slow down ice accumulation, while easier diffusion of molecules on weakly polar ices promotes the production of carbon dioxide. Efficient chemical desorption from bare grains significantly delays the appearance of the first ice monolayer. Conclusions. The combination of multiple aspects of grain surface chemistry creates a gas-ice balance that is different from simpler models. The composition of the interstellar ices is regulated by several binding-energy dependent desorption mechanisms. Their actions overlap in time and space, explaining the similar proportions of major ice components (water and carbon oxides) observed in all directions. [ABSTRACT FROM AUTHOR]

Context. The presence of grains is key to the synthesis of molecules in the interstellar medium that cannot form in the gas phase due to its low density and temperature conditions. In these reactions, the role of the grains is to enhance the encounter rate of the reactive species on their surfaces and to dissipate the energy excess of largely exothermic reactions, but less is known about their role as chemical catalysts; namely, bodies that provide low activation energy pathways with enhanced reaction rates. Different refractory materials with catalytic properties, such as those containing space-abundant d-block transition metals like iron (Fe), are present in astrophysical environments. Aims. Here, we report for first time mechanistic insights into the Fischer-Tropsch-type (FTT) synthesis of ethanol (CH3CH2OH), through ketene (CH2CO) and acetaldehyde (CH3CHO) intermediates, and methane (CH4) via a chain growing mechanism using a single-Fe atom supported on silica (SiO2) surfaces as a heterogeneous astrocatalyst. Methods. Quantum chemical simulations based on extended periodic surfaces were carried out to characterize the potential energy surfaces of the FTT chain growing mechanism. Calculations of the binding energies of reaction intermediates and products and Rice–Ramsperger–Kassel–Marcus kinetic calculations were performed to evaluate catalytic efficiencies and determine the feasibility of the reactions in different astrophysical environments. Results. Mechanistic studies demonstrate that the FTT chain growing mechanism enters into direct competition with FTT methanol formation, since formation of the CH2 chain growth initiator is feasible. The coupling of the CH2 with CO (forming ketene) and subsequent H2 additions yield acetaldehyde and finally ethanol, while direct H2 addition to CH2 produces methane. Thermodynamically, both processes are largely exergonic, but they present energy barriers that require external energy inputs to be overcome. Kinetic calculations demonstrate the strong temperature dependency of the FTT processes as tunneling does not dominate. Conclusions. The results could explain the presence of CH3CH2OH and CH4 in diverse astrophysical regions where current models fail to reproduce their observational quantities. The evidence that the chain growing mechanism is operating opens a new reactivity paradigm toward the formation of complex organic molecules, which is constrained by the temperature-dependent behaviour of the FTT reactions and by making their energy features a crucial aspect. [ABSTRACT FROM AUTHOR]

This study presents calculations for cross sections of the vibrational excitation of H2O(X1A1) via electron impact. The theoretical approach employed here is based on first principles only, combining electron-scattering calculations performed using the UK R-matrix codes for several geometries of the target molecule, three-dimensional (3D) vibrational states of H2O, and 3D vibrational frame transformation. The aim is to represent the scattering matrix for the electron incident of the molecule. The vibrational wave functions were obtained numerically, without the normal-mode approximation, so that the interactions and transitions between vibrational states assigned to different normal modes could be accounted for. The thermally averaged rate coefficients were derived from the calculated cross sections for temperatures in the 10–10 000 K interval and analytical fits for rate coefficients were also provided. We assessed the uncertainty estimations of the obtained data for subsequent applications of the rate coefficients in modelling the non-local thermal equilibrium (non-LTE) spectra of water in various astrophysical environments. [ABSTRACT FROM AUTHOR]

Aims. Astrophysical ices on dust grain mantles in the interstellar medium (ISM) and dense circumstellar envelopes (CSEs) are continuously exposed to galactic cosmic rays (GCRs). In a laboratory setting, we studied the physical and chemical modifications of ice layers induced by energetic heavy ions as GCR analogues. The ice layers used have a molecular composition similar to that of icy grain mantles. Methods. Mixtures of H2O:CO:CH3OH molecules (percentages 73:24:3, 68:30:3, and 58:38:3) were condensed on a substrate at 15 K and irradiated with 40 MeV 58Ni11+ ion beams. Irradiation-induced modifications were followed using the mid-infrared absorption spectroscopy technique. Results. We observed the evolution of infrared bands of CO2, HCO, HCOOH, CH4, H2CO,H2O2, and more complex synthesised molecules. From the molecular column densities, cross-sections and sputtering yields were determined and compared to published results of water and carbon monoxide. Analysis of the chemical modifications reveals that the precursors are easily destroyed when they are in a molecular mixture, while others are desorbed. Conclusions. The main radiolitic modifications induced by GCR irradiations are molecular decomposition and sputtering. Extrapolation to astrophysical radiation conditions shows a strong dependence on the intensity of the GCR distributions at low energies, which allows the analysis of the ice evolution at timescales comparable to those of the ISM and CSE. [ABSTRACT FROM AUTHOR]

Context. The solid-state C2H2 chemistry in interstellar H2O-rich ice has been proposed to explain astronomically observed complex organic molecules (COMs), including ketene (CH2CO), acetaldehyde (CH3CHO), and ethanol (CH3CH2OH), toward early star-forming regions. This formation mechanism is supported by recent laboratory studies and theoretical calculations for the reactions of C2H2+OH/H. However, the analog reaction of C2H2+NH2 forming N-bearing species has been suggested to have a relatively low rate constant that is orders of magnitude lower than the value of C2H2+OH. Aims. This work extends our previous laboratory studies on O-bearing COM formation to investigate the interactions between C2H2 and NH3 ice triggered by cosmic ray-induced secondary UV photons under molecular cloud conditions. Methods. Experiments were performed in an ultra-high vacuum chamber to investigate the UV photolysis of the C2H2:NH3 ice mixture at 10 K. The ongoing chemistry was monitored in situ by Fourier-transform infrared spectroscopy as a function of photon fluence. The IR spectral identification of the newly formed N-bearing products was further secured by a quadrupole mass spectrometer during the temperature-programmed desorption experiment. Results. The studied ice chemistry of C2 H2 with NH2 radicals and H atoms resulting from the UV photodissociation of NH3 leads to the formation of several N-bearing COMs, including vinylamine (CH2CHNH2), acetaldimine (CH3CHNH), acetonitrile (CH3CN), ketenimine (CH2CNH), and tentatively ethylamine (CH3CH2NH2). The experimental results show an immediate and abundant CH2CHNH2 yield as the first-generation product, which is further converted into other chemical derivatives. The effective destruction and formation cross-section values of parent species and COMs were derived, and we discuss the chemical links among these molecules and their astronomical relevance. [ABSTRACT FROM AUTHOR]

Context. Among the silicon-bearing species discovered in the interstellar medium, SiS and SiO stand out as key tracers due to their distinct chemistry and variable abundances in interstellar and circumstellar environments. Nevertheless, while the origins of SiO are well documented, the SiS chemistry remains relatively unexplored. Aims. Our objective is to enhance the network of Si- and S-bearing chemical reactions for a gas-grain model in molecular clouds, encompassing both low and high metallicities. To achieve this, we calculated the energies and rate coefficients for six neutral atom-diatom reactions involved in the SiCS triatomic system, with a special focus on the C+SiS and S+SiC collisions. Methods. We employed the coupled-cluster method with single and double substitutions and a perturbative treatment of triple substitutions (CCSD(T)) refined at the explicitly correlated CCSD(T)-F12 level. With these computational results in conjunction with supplementary data from the literature, we construct an extended network of neutral-neutral chemical reactions involving Si- and S-bearing molecules. To assess the impact of these chemical reactions, we performed time-dependent models employing the Nautilus gas-grain code, setting the gas temperature to 10 K and the H2 density to 2 × 104 cm−3. The models considered two initial abundance scenarios, corresponding to low- and high-metallicity levels. Abundances were computed using both the default chemical network and the constrained network, enriched with newly calculated reactions. Results. The temperature dependence for the reactions involving SiS were modelled to the k(T) = α (T/300)β exp (−γ/T) expression, and the coefficients are provided for the first time. The high-metallicity models significantly boost the SiS production, resulting in abundances nearly four orders of magnitude higher compared to low-metallicity models. Higher initial abundances of C, S, and Si, roughly ~2, 190, and 210 times higher, respectively, contribute to this. Around the age of 103 yr, destruction mechanisms become relevant, impacting the abundance of SiS. The proposed production reaction S + SiC → C + SiS, mitigates these effects in later stages. By expanding the gas reaction network using a high-metallicity model, we derived estimates for the abundances of observed interstellar molecules, including SiO, SO, and SO2. Conclusions. We demonstrate the significance of both SiC+S and C+SiS channels in the SiS chemistry. Notably, the inclusion of neutral-neutral mechanisms, particularly via Si+HS and S+SiC channels, played a pivotal role in determining SiS abundance. These mechanisms carry a significance level on a par with that of the well-known and fast ion-neutral reactions. [ABSTRACT FROM AUTHOR]

Aims. A series of high-precision calculations for the electronic structure of MgH have been reported in the past two decades; however, most of them d not include the core-valence correlation and still exhibit distinct differences. Furthermore, the latest high-precision results have not been applied to the studies of photodissociation dynamics. The primary motivations of this paper are to calculate a more precise electronic structure of MgH consering a core-valence correlation and to prove the photodissociation cross-sections. Methods. The electronic structure of MgH is investigated by multi-reference configuration interaction calculations with Davson correction (MRCI+Q). We performed two different sets of calculations to investigate the core-valence correlation and, as a result, obtained accurate potential energy curves (PECs) and transition dipole moments (TDMs). An extrapolation procedure was also employed to eliminate the error of basis set. Then, the photodissociation cross-sections were calculated using high-precision PECs and TDMs. Results. The PECs and TDMs of the five lowest doublet electronic states, X2Σ+, B′2Σ+, E2Σ+, A2Π, and C2Π, are obtained from calculations including core-valence correlation, termed as CV-MRCI, while PECs of the ten lowest doublet states and three quartet states are also obtained from NCV-MRCI calculations without core-valence correlation. The spectroscopic constants and band oscillator strengths are also proved with high precision levels. The equilibrium Re and vertical excitation energy Te are only 0.1% different from the measurements. Based on the CV-MRCI results, the rovibrationally resolved photodissociation cross-sections for transitions from X2Σ+ to the other four states, as well as the total local thermodynamic equilibrium cross-sections for temperatures up to 10000 K, are calculated. [ABSTRACT FROM AUTHOR]

Context. The inner few AU of disks around young stars, where terrestrial planets are thought to form, are best probed in the infrared. The James Webb Space Telescope is now starting to characterize the chemistry of these regions in unprecedented detail, building on earlier results of the Spitzer Space Telescope that the planet-forming zone of disks contain a rich chemistry. One peculiar subset of sources characterized by Spitzer are the so-called CO2-only sources, in which only a strong 15 μm CO2 feature was detected in the spectrum. Aims. One scenario that could explain the weak or even non-detections of molecular emission from H2O is the presence of a small, inner cavity in the disk. If this cavity were to extend past the H2O snowline, but not past the CO2 snowline, this could strongly suppress the H2O line flux with respect to that of CO2. For this work, we aimed to test the validity of this statement. Methods. Using the thermo-chemical code Dust And LInes (DALI), we created a grid of T Tauri disk models with an inner cavity, meaning we fully depleted the inner region of the disk in gas and dust starting from the dust sublimation radius and ranging until a certain cavity radius. Cavity radii varying in size from 0.1 to 10 AU were explored for this work. We extended this analysis to test the influence of cooling through H2O ro-vibrational lines and the luminosity of the central star on the CO2 /H2O flux ratio. Results. We present the evolution of the CO2 and H2O spectra of a disk with inner cavity size. The line fluxes show an initial increase as a result of an increasing emitting area, followed by a sharp decrease. As such, when a large-enough cavity is introduced, a spectrum that was initially dominated by H2O lines can become CO2-dominated instead. However, the cavity size needed for this is around 4–5 AU, exceeding the nominal position of the CO2 snowline in a full disk, which is located at 2 AU in our fiducial, L* = 1.4 L⊙ model. The cause of this is most likely the alteration of the thermal structure by the cavity, which pushes the snowlines outward. In contrast, our models show that global temperature fluctuations, for example due to changes in stellar luminosity, impact the fluxes of H2O and CO2 roughly equally, thus not impacting their ratio much. Alternative explanations for bright CO2 emission are also briefly discussed. Conclusions. Our modeling work shows that it is possible for the presence of a small inner cavity to explain strong CO2 emission in a spectrum. However, the cavity needed to do so is larger than what was initially expected. As such, this scenario will be easier to test with sufficiently high angular resolution (millimeter) observations. [ABSTRACT FROM AUTHOR]

Context. Galactic cosmic rays (CRs) play a crucial role in ionisation, dissociation, and excitation processes within dense cloud regions where UV radiation is absorbed by dust grains and gas species. CRs regulate the abundance of ions and radicals, leading to the formation of more and more complex molecular species, and determine the charge distribution on dust grains. A quantitative analysis of these effects is essential for understanding the dynamical and chemical evolution of star-forming regions. Aims. The CR-induced photon flux has a significant impact on the evolution of the dense molecular medium in its gas and dust components. This study evaluates the flux of UV photons generated by CRs to calculate the photon-induced dissociation and ionisation rates of a vast number of atomic and molecular species, as well as the integrated UV photon flux. Methods. To achieve these goals, we took advantage of recent developments in the determination of the spectra of secondary electrons, in the calculation of state-resolved excitation cross sections of H2 by electron impact, and of photodissociation and photoionisation cross sections. Results. We calculated the H2 level population of each rovibrational level of the X, B, C, B′, D, B″, D′, and a states. We then computed the UV photon spectrum of H2 in its line and continuum components between 72 and 700 nm, with unprecedented accuracy, as a function of the CR spectrum incident on a molecular cloud, the H2 column density, the isomeric H2 composition, and the dust properties. The resulting photodissociation and photoionisation rates are, on average, lower than previous determinations by a factor of about 2, with deviations of up to a factor of 5 for the photodissociation of species such as AlH, C2H2, C2H3, C3H3, LiH, N2, NaCl, NaH, O2+, S2, SiH, l-C4, and l-C5H. A special focus is given to the photoionisation rates of H2, HF, and N2, as well as to the photodissociation of H2, which we find to be orders of magnitude higher than previous estimates. We give parameterisations for both the photorates and the integrated UV photon flux as a function of the CR ionisation rate, which implicitly depends on the H2 column density, as well as the dust properties. [ABSTRACT FROM AUTHOR]

Context. Indene, a small PAH, has been detected in the gas phase in the cold dense cloud TMC-1. Due to the low temperature in the cloud, below indene condensation temperature, its presence in the ice mantles of dust grains is likely. Aims. The aim of this work is to study the stability of indene against the energetic processing by VUV photons or cosmic rays in the ice mantles of dense molecular clouds. Methods. Ice layers of pure indene or indene diluted in water ice were grown by vapor deposition on a cold surface held at 10 K, 100 K, or 140 K. The samples were processed with VUV photons (120–180 nm) and 5 keV electrons and the destruction of indene was monitored by following the decay of its absorption bands in the infrared (IR) spectrum. Finally, we recorded the mass spectra of the decomposition products sublimated by thermal programmed desorption of the processed samples. Results. Photolysis and radiolysis cross-sections, along with half-life energy doses for indene in the solid form and diluted in water ice matrices at 10 K were derived. Ketones and alcohols were identified as the main processing products in indene and water–ice mixtures Conclusions. Dilution in water ice enhances the destruction rate of indene under energetic processing. The molecule is expected to survive for more than 107 yr in the ice mantles of grains in the interior of dense clouds, but it will end up getting destroyed within the next few hundred years by the intense VUV field in the diffuse region at the edges of the cloud. [ABSTRACT FROM AUTHOR]

Context. Detailed astrochemical models are a key component to interpret the observations of interstellar and circumstellar molecules since they allow important physical properties of the gas and its evolutionary history to be deduced. Aims. We update one of the most widely used astrochemical databases to reflect advances in experimental and theoretical estimates of rate coefficients and to respond to the large increase in the number of molecules detected in space since our last release in 2013. Methods. We present the sixth release of the UMIST Database for Astrochemistry (UDfA), a major expansion of the gas-phase chemistry that describes the synthesis of interstellar and circumstellar molecules. Since our last release, we have undertaken a major review of the literature which has increased the number of reactions by over 40% to a total of 8767 and increased the number of species by over 55% to 737. We have made a particular attempt to include many of the new species detected in space over the past decade, including those from the QUIJOTE and GOTHAM surveys, as well as providing references to the original data sources. Results. We use the database to investigate the gas-phase chemistries appropriate to both O-rich and C-rich conditions in TMC-1 and to the circumstellar envelope of the C-rich AGB star IRC+10216 and identify successes and failures of gas-phase only models. Conclusions. This update is a significant improvement to the UDfA database. For both the dark cloud and C-rich circumstellar envelope models, calculations match around 60% of the abundances of observed species to within an order of magnitude. There are a number of detected species, however, that are not included in the model either because their gas-phase chemistry is unknown or because they are likely formed via surface reactions on icy grains. Future laboratory and theoretical work is needed to include such species in reaction networks. [ABSTRACT FROM AUTHOR]

Context. Nitrogen-bearing molecules (such as N2H+ and NH3) are excellent tracers of high-density and low-temperature regions, such as dense cloud cores. Notably, they could help advance the understanding of snow lines in protoplanetary discs and the chemical evolution of comets. However, much remains unknown about the chemistry of N-bearing molecules on grain surfaces, which could play an important role in their formation and evolution. Aims. In this work, we experimentally study the behaviour of NH3 on surfaces that mimic grain surfaces under interstellar conditions in the presence of some other major components of interstellar ices (i.e. H2O, CO2, CO). We measure the binding energy distributions of NH3 from different H2O ice substrates and also investigate how it could affect the NH3 snow line in protoplanetary discs. Methods. We performed laboratory experiments using the ultra-high vacuum (UHV) set-up VENUS (VErs des NoUvelles Syntheses). We co-deposited NH3 along with other adsorbates (H2O, 13CO, and CO2) and performed temperature programmed desorption (TPD) and temperature programmed-during exposure desorption (TP-DED) experiments. The experiments were monitored using a quadrupole mass spectrometer and a Fourier transform reflection absorption infrared spectrometer (FT-RAIRS). We obtained the binding energy distribution of NH3 on crystalline ice (CI) and compact amorphous solid water ice by analysing the TPD profiles of NH3 obtained after depositions on these substrates. Results. In the co-deposition experiments, we observed a significant delay in the desorption and a decrease of the desorption rate of NH3 when H2O is introduced into the co-deposited mixture of NH3–13CO or NH3–CO2, which is not the case in the absence of H2O. Secondly, we noticed that H2O traps roughly 5–9% of the co-deposited NH3, which is released during the phase change of water from amorphous to crystalline. Thirdly, we obtained a distribution of binding energy values of NH3 on both ice substrates instead of an individual value, as assumed in previous works. For CI, we obtained an energy distribution between 3780 K and 4080 K, and in the case of amorphous ice, the binding energy values were distributed between 3630 K and 5280 K; in both cases we used a pre-exponential factor of A = 1.94 × 1015 s−1. Conclusions. From our experiments, we conclude that the behaviour of NH3 is significantly influenced by the presence of water, owing to the formation of hydrogen bonds with water, in line with quantum calculations. This interaction, in turn, preserves NH3 on the grain surfaces longer and up to higher temperatures, making it available closer to the central protostar in protoplanetary discs than previously thought. It explains well why the NH3 freeze-out in pre-stellar cores is efficient. When present along with H2O, CO2 also appears to impact the behaviour of NH3, retaining it at temperatures similar to those of water. This may impact the overall composition of comets, particularly the desorption of molecules from their surface as they approach the Sun. [ABSTRACT FROM AUTHOR]

We present new observations of molecular anions with the Yebes 40 m and IRAM 30 m telescopes toward the cold, dense clouds TMC-1 CP, Lupus-1A, L1527, L483, L1495B, and L1544. We report the first detections of C3N− and C5N− in Lupus-1A as well as C4H− and C6H− in L483. In addition, we detected new lines of C6H− toward the six targeted sources, of C4H− toward TMC-1 CP, Lupus-1A, and L1527, and of C8H− and C3N− in TMC-1 CP. Excitation calculations using recently computed collision rate coefficients indicate that the lines of anions accessible to radiotelescopes run from subthermally excited to thermalized as the size of the anion increases, with the degree of departure from thermalization depending on the H2 volume density and the line frequency. We noticed that the collision rate coefficients available for the radical C6H are not sufficient to explain various observational facts, thereby calling for the collision data for this species to be revisited. The observations presented here, together with observational data from the literature, have been used to model the excitation of interstellar anions and to constrain their abundances. In general, the anion-to-neutral ratios derived here agree with the literature values, when available, within 50% (by a factor of two at most), except for the C4H−/C4H ratio, which shows higher differences due to a revision of the dipole moment of C4H. From the set of anion-to-neutral abundance ratios derived two conclusions can be drawn. First, the C6H−/C6H ratio shows a tentative trend whereby it increases with increasing H2 density, as we would expect on the basis of theoretical grounds. Second, the assertion that the higher the molecular size, the higher the anion-to-neutral ratio is incontestable; furthermore, this supports a formation mechanism based on radiative electron attachment. Nonetheless, the calculated rate coefficients for electron attachment to the medium size species C4H and C3N are probably too high and too low, respectively, by more than one order of magnitude. [ABSTRACT FROM AUTHOR]

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

Context. Carbon monosulphide (CS) is among the few sulphur-bearing species that have been widely observed in all environments, including in the most extreme, such as diffuse clouds. Moreover, CS has been widely used as a tracer of the gas density in the interstellar medium in our Galaxy and external galaxies. Therefore, a complete understanding of its chemistry in all environments is of paramount importance for the study of interstellar matter. Aims. Our group is revising the rates of the main formation and destruction mechanisms of CS. In particular, we focus on those involving open-shell species for which the classical capture model might not be sufficiently accurate. In this paper, we revise the rates of reactions CH + S → CS + H and C2 + S → CS + C. These reactions are important CS formation routes in some environments such as dark and diffuse warm gas. Methods. We performed ab initio calculations to characterize the main features of all the electronic states correlating to the open shell reactants. For CH+S, we calculated the full potential energy surfaces (PESs) for the lowest doublet states and the reaction rate constant with a quasi-classical method. For C2+S, the reaction can only take place through the three lower triplet states, which all present deep insertion wells. A detailed study of the long-range interactions for these triplet states allowed us to apply a statistic adiabatic method to determine the rate constants. Results. Our detailed theoretical study of the CH + S → CS + H reaction shows that its rate is nearly independent of the temperature in a range of 10–500 K, with an almost constant value of 5.5 × 10−11 cm3 s−1 at temperatures above 100 K. This is a factor of about 2–3 lower than the value obtained with the capture model. The rate of the reaction C2 + S → CS + C does depend on the temperature, and takes values close to 2.0 × 10−10 cm3 s−1 at low temperatures, which increase to ~ 5.0 × 10−10 cm3 s−1 for temperatures higher than 200 K. In this case, our detailed modeling - taking into account the electronic and spin states – provides a rate that is higher than the one currently used by factor of approximately 2. Conclusions. These reactions were selected based on their inclusion of open-shell species with many degenerate electronic states, and, unexpectedly, the results obtained in the present detailed calculations provide values that differ by a factor of about 2–3 from the simpler classical capture method. We updated the sulphur network with these new rates and compare our results in the prototypical case of TMC1 (CP). We find a reasonable agreement between model predictions and observations with a sulphur depletion factor of 20 relative to the sulphur cosmic abundance. However, it is not possible to fit the abundances of all sulphur-bearing molecules better than a factor of 10 at the same chemical time. [ABSTRACT FROM AUTHOR]

Context. The nondissociative ultraviolet photodesorption of water ice is a nonthermal desorption mechanism required to account for detected abundances of gas-phase water toward cold regions within the interstellar medium. Previous experimental and theoretical studies provide a range of photodesorption rates for H2O ice and point to a convoluted competition with other molecular processes following the absorption of a UV photon in the ice. Ultraviolet irradiation also induces photodissociation, resulting in the formation of radicals that may directly desorb triggering gas-phase reactions or recombine in surface reactions. Aims. In this work, we aim to quantify the effects of photodesorption and investigate photoconversion upon UV photolysis of an H2O ice. Methods. We irradiated a porous amorphous H2O ice at 20 K with UV photons in the 7–10.2 eV range and compared the measurements to a nearly identical experiment that included a layer of argon coating on top of the water ice. The purpose of the argon coating is to quench any type of photon-triggered desorption. To trace ice composition and thickness, laser desorption post ionization time-of-flight mass spectrometry was utilized. This method is independent of the (non)dissociative character of a process and provides a diagnostic tool different from earlier studies that allows an independent check. Results. The total photodesorption rate for a porous amorphous H2O ice at 20 K we derive is (1.0 ± 0.2) × 10−3 per incident UV photon (7–10.2 eV), which is in agreement with the available literature. This rate is based on the elemental balance of oxygen-bearing species. As a result, we placed an upper limit on the intact (H2O) and dissociative (OH) desorption rates equal to 1.0 × 10−3 per incident UV photon, while for the reactive desorption (O2), this limit is equal to 0.5 × 10−3 per incident UV photon. Photoconversion depletes the H2O ice at a rate of (2.3 ± 0.2) × 10−3 per incident UV photon. At low UV fluence (9.0 × 1017 photons cm−2), the loss of H2O is balanced by photoproduct formation (O2 and H2O2). At high UV fluence (4.5 × 1018 photons cm−2), about 50% of the initial H2O molecules are depleted. This amount is not matched by the registered O-bearing products, which points to an additional, unaccounted loss channel of H2O. [ABSTRACT FROM AUTHOR]

We investigate the radiative association of SiO+ in the collision of a Si+(3s23p 2Pu) cation and an O(2s22p4 3Pg) atom using the quantum mechanical method, including the cross sections and rate coefficients. We consider 18 dipole-allowed radiative association processes of SiO+. The results show that the 2 2A 2transition contributes most for the SiO+ radiative association at temperatures from 10 to 10 000 K. The 2 2X 2S+ and 2 2S-A 2s transitions are also relatively significant at high temperatures. The total rate coefficient is found to vary from 7.72 × 10-18 to 4.92 × 10-17 cm3 s-1. Finally, an analytical function is fitted to the total rate coefficient for the convenience of astrochemical modelling. The obtained cross sections and rate coefficients are expected to be useful for modelling the Si chemistry in the diffuse interstellar medium. [ABSTRACT FROM AUTHOR]

We investigate the radiative association of SiO+ in the collision of a Si+(3s23p 2Pu) cation and an O(2s22p4 3Pg) atom using the quantum mechanical method, including the cross sections and rate coefficients. We consider 18 dipole-allowed radiative association processes of SiO+. The results show that the 2 2A 2transition contributes most for the SiO+ radiative association at temperatures from 10 to 10 000 K. The 2 2X 2S+ and 2 2S-A 2s transitions are also relatively significant at high temperatures. The total rate coefficient is found to vary from 7.72 × 10-18 to 4.92 × 10-17 cm3 s-1. Finally, an analytical function is fitted to the total rate coefficient for the convenience of astrochemical modelling. The obtained cross sections and rate coefficients are expected to be useful for modelling the Si chemistry in the diffuse interstellar medium. [ABSTRACT FROM AUTHOR]

Aims. The detection of c-C3HC2H and possible future detection of c-C3HCN provide new molecules for reaction chemistry in the dense interstellar medium (ISM) where R-C2H and R-CN species are prevalent. Determination of chemically viable c-C3HC2H and c-C3HCN derivatives and their prominent spectral features can accelerate potential astrophysical detection of this chemical family. This work characterizes three such derivatives: c-C3(C2H)2, c-C3(CN)2, and c-C3(C2H)(CN). Methods. Interstellar reaction pathways of small carbonaceous species are well replicated through quantum chemical means. Highly accurate cc-pVXZ-F12/CCSD(T)-F12 (X = D,T) calculations generate the energetics of chemical formation pathways as well as the basis for quartic force field and second-order vibrational perturbation theory rovibrational analysis of the vibrational frequencies and rotational constants of the molecules under study. Results. The formation of c-C3(C2H)2 is as thermodynamically and, likely, as stepwise favorable as the formation of c-C3HC2H, rendering its detectability to be mostly dependent on the concentrations of the reactants. Both c-C3(C2H)2 and c-C3(C2H)(CN) will be detectable through radioastronomical observation with large dipole moments of 2.84 D and 4.26 D, respectively, while c-C3(CN)2 has an exceedingly small and likely unobservable dipole moment of 0.08 D. The most intense frequency for c-C3(C2H)2 is v2 at 3316.9 cm–1 (3.01 μm), with an intensity of 140 km mol–1. The mixed-substituent molecule c-C3(C2H)(CN) has one frequency with a large intensity, v1, at 3321.0 cm–1 (3.01 μm), with an intensity of 82 km mol–1. The molecule c-C3(CN)2 lacks intense vibrational frequencies within the range that current instrumentation can readily observe. Conclusions. Both c-C3(C2H)2 and c-C3(C2H)(CN) are viable candidates for astrophysical observation, with favorable reaction profiles and spectral data produced herein, but c-C3(CN)2 will not be directly observable through any currently available remote sensing means, even if it forms in large abundances. [ABSTRACT FROM AUTHOR]

Context. Very small grains and large hydrocarbon molecules are known to convert a fraction of the ultraviolet (UV) and visible stellar radiation to near- and mid-infrared (IR) photons via stochastic heating and subsequent radiative de-excitation. However, no convincing explanation for the near-IR continuum emission observed in some reflection nebulae and planetary nebulae has been provided so far. Aims. We aim to investigate the extent that recurrent fluorescence originating from stellar photon absorption by Cn (n = 24, 42, 60) carbon clusters can account for the IR emission detected in various interstellar environments. To this aim, we modelled the collective emission signature of a carbon cluster sample induced by irradiation from a 20 000 K blackbody source. From the obtained results, we set out to determine the fraction of interstellar carbon locked up in the emitting objects. Methods. The collective emission signature was computationally determined for different structural families encompassing cages, flakes, pretzels, and branched isomers by means of a kinetic Monte Carlo stochastic approach based on harmonic vibrational densities of states. The collective emission spectra result from the overall radiative cooling of a large population of neutral carbon clusters, during which recurrent fluorescence and vibrational emission compete with each other. Results. Our modelling shows that recurrent fluorescence from C60 cages and flakes (with little or no sp1 carbon atoms) and C42 cages are able to explain the near-IR continuum emission observed in several reflection nebulae and planetary nebulae. Assuming that the continuum emission observed towards NGC 7023 is due to recurrent fluorescence induced by UV or visible photon absorption in neutral cage carbon clusters containing about 30–60 atoms, the carriers contain about 0.1–1.5% of the interstellar carbon abundance. [ABSTRACT FROM AUTHOR]

Aims. With this article, we aim to provide the sputtering yields for molecular species of potential astrophysical interest and in the electronic regime of interaction characteristic of cosmic rays. We specifically target molecules that are constitutive of interstellar ice mantles. Methods. We used a compendium of existing data on electronic sputtering to calculate the prefactors leading to the generalisation of the stopping-power-dependent sputtering yield for many species condensing at low temperature. In addition, we present new experimental results to constrain the yield for solid CH4, C6, and CH3CN. Results. Electronic sputtering is constrained using literature data for H2, HD, D2, Ne, N2, CO, Ar, O2, Kr, Xe, CO2, SO2, NH3, S, H2O, D2O, CH3OH, Leucine, C20H12, C24H12, and C60. A first-order relation with the sublimation enthalpy is derived, which allows us to predict the sputtering yield within an order of magnitude for most species. The fluctuations around the mean are partly assignable to the differences in resilience towards radiolysis for individual species, and partly to the micro-physics details of the energy transfer to the lattice. [ABSTRACT FROM AUTHOR]

Context. Water photodissociation in the 114–143 nm UV range forms excited OH which emits at mid-infrared (MIR) wavelengths via highly excited rotational lines. These lines have only been detected with Spitzer in proto-planetary disks and shocks. Previous studies have shown that they are a unique diagnostic for water photodissociation. Thanks to its high sensitivity and angular resolution, the James Webb Space Telescope (JWST) could be able to detect them in other environments such as interstellar photodissociation regions (PDRs). Aims. Our goal is to predict OH MIR lines for a large range of thermal pressures and UV fields in PDRs. Methods. We use the Meudon PDR Code to compute the thermal and chemical structure of PDRs. In order to predict the emerging spectrum of OH, we amended the code to include prompt emission induced by H2O photodissociation between 114 and 143 nm. We performed a detailed study of the influence of thermal pressure (Pth/k = nHTK) and UV field strength on the integrated intensities and their detectability with the JWST. Results. OH MIR emission is predicted to originate very close to the H0/H2 transition and is directly proportional to the column density of water photodissociated in that layer. Because gas-phase neutral-neutral reactions forming water require relatively high temperatures (TK ≳ 300 K), the resulting OH MIR lines are primarily correlated with the temperature at this position, and are therefore brighter in regions with high pressure. This implies that these lines are predicted to be only detectable in strongly irradiated PDRs (G0incident > 103) with high thermal pressure (Pth/k ≳ 5x107 K cm–3). In the latter case, OH MIR lines are less dependent on the strength of the incident UV field. The detection of such lines in PDRs such as the Orion bar – which should be possible – is also investigated and we show that the line-to-continuum ratio could be a major limitation for detection because of instrumental limitations. Conclusions. OH MIR lines observable by JWST are a promising diagnostic for dense and strongly irradiated PDRs and proplyds. Their intensities are directly proportional to the amount of water photodissociated and they are therefore an indirect but sensitive probe of the gas temperature at the H0/H2 transition. [ABSTRACT FROM AUTHOR]

Context. The study of the early phases of star and planet formation is important to understand the physical and chemical history of stellar systems such as our own. In particular, protostars born in rich clusters are prototypes of the young Solar System. Aims. In the framework of the Seeds Of Life In Space (SOLIS) large observational project, the aim of the present work is to investigate the origin of the previously inferred high flux of energetic particles in the protocluster FIR4 of the Orion Molecular Cloud 2 (OMC-2), which appears asymmetric within the protocluster itself. Methods. Interferometric observations carried out with the IRAM NOEMA interferometer were used to map the silicon monoxide (SiO) emission around the FIR4 protocluster. Complementary archival data from the ALMA interferometer were also employed to help constrain excitation conditions. A physical-chemical model was implemented to characterise the particle acceleration along the protostellar jet candidate, along with a non-LTE analysis of the SiO emission along the jet. Results. The emission morphology of the SiO rotational transitions hints for the first time at the presence of a collimated jet originating very close to the brightest protostar in the cluster, HOPS-108. Conclusions. The NOEMA observations unveiled a possible jet in the OMC-2 FIR4 protocluster propagating towards a previously measured enhanced cosmic-ray ionisation rate. This suggests that energetic particle acceleration by the jet shock close to the protostar might be at the origin of the enhanced cosmic-ray ionisation rate, as confirmed by modelling the protostellar jet. [ABSTRACT FROM AUTHOR]

The formation of hydrides by gas-phase reactions between H2 and a heavy element atom is a very selective process. Reactions with ground-state neutral carbon, oxygen, nitrogen, and sulfur atoms are very endoergic and have high energy barriers because the H2 molecule has to be fragmented before a hydride bond is formed. In cold interstellar clouds, these barriers exclude the formation of CH, OH, NH, and SH radicals through hydrogen abstraction reactions. Here we study a very energetically unfavorable process, the reaction of N(4S) atoms with H2 molecules. We calculated the reaction rate coefficient for H2 in different vibrational levels, using quantum methods for v = 0−7 and quasi-classical methods up to v =12; for comparison purposes, we also calculated the rate coefficients of the analogous reaction S (3P)+ H2(v) → SH + H. Owing to the high energy barrier, these rate coefficients increase with v and also with the gas temperature. We implemented the new rates in the Meudon photodissociation region (PDR) code and studied their effect on models with different ultraviolet (UV) illumination conditions. In strongly UV-irradiated dense gas (Orion Bar conditions), the presence of H2 in highly vibrationally excited levels (v ≥ 7) enhances the NH abundance by two orders of magnitude (at the PDR surface) compared to models that use the thermal rate coefficient for reaction N(4S) + H2 → NH + H. The increase in NH column density, N(NH), across the PDR is a factor of ~25. We investigate the excitation and detectability of submillimeter NH rotational emission lines. Being a hydride, NH excitation is very subthermal (Trot ≪ Tk) even in warm and dense gas. We explore existing Herschel/HIFI observations of the Orion Bar and Horsehead PDRs. We report a 3σ emission feature at the ~974 GHz frequency of the NH NJ = 12 − 01 line toward the Bar. The emission level implies N(NH) ≃ 1013 cm−2, which is consistent with PDR models using the new rate coefficients for reactions between N and UV-pumped H2. This formation route dominates over hydrogenation reactions involving the less abundant N+ ion. JWST observations will quantify the amount and reactivity of UV-pumped H2 in many interstellar and circumstellar environments. [ABSTRACT FROM AUTHOR]

Context. Carbonic acid (H2CO3) is a weak acid relevant to astrobiology which, to date, remains undetected in space. Experimental work has shown that the β-polymorph of H2CO3 forms under space relevant conditions through energetic (UV photon, electron, and cosmic ray) processing of CO2- and H2O-rich ices. Although its α-polymorph ice has been recently reassigned to the monomethyl ester of carbonic acid, a different form of H2CO3 ice may exist and is synthesized without irradiation through surface reactions involving CO molecules and OH radicals, that is to say γ-H2CO3. Aims. We aim to provide a systematic set of vacuum ultraviolet (VUV) photoabsorption spectroscopic data of pure carbonic acid that formed and was destroyed under conditions relevant to space in support of its future identification on the surface of icy objects in the Solar System by the upcoming Jupiter ICy moons Explorer mission and on interstellar dust by the James Webb Space Telescope spacecraft. Methods. We present VUV photoabsorption spectra of pure and mixed CO2 and H2O ices exposed to 1 keV electrons at 20 and 80 K to simulate different interstellar and Solar System environments. Ices were then annealed to obtain a layer of pure H2CO3 which was further exposed to 1 keV electrons at 20 and 80 K to monitor its destruction pathway. Fourier-transform infrared (FT-IR) spectroscopy was used as a secondary probe providing complementary information on the physicochemical changes within an ice. Results. Our laboratory work shows that the formation of solid H2CO3, CO, and O3 upon the energetic processing of CO2:H2O ice mixtures is temperature-dependent in the range between 20 and 80 K. The amorphous to crystalline phase transition of H2CO3 ice is investigated for the first time in the VUV spectral range by annealing the ice at 200 and 225 K. We have detected two photoabsorption bands at 139 and 200 nm, and we assigned them to β-H2CO3 and γ-H2CO3, respectively. We present VUV spectra of the electron irradiation of annealed H2CO3 ice at different temperatures leading to its decomposition into CO2, H2O, and CO ice. Laboratory results are compared to Cassini UltraViolet Imaging Spectrograph observations of the 70−90 K ice surface of Saturn's satellites Enceladus, Dione, and Rhea. [ABSTRACT FROM AUTHOR]

Context. Nonlinear behavior in interstellar chemical models has been recognized for 25 years now. Different mechanisms account for the possibility of multiple fixed-points at steady-state, characterized by the ionization degree of the gas. Aims. Chemical oscillations are also a natural behavior of nonlinear chemical models. We study under which conditions spontaneous sustained chemical oscillations are possible, and what kind of bifurcations lead to, or quench, the occurrence of such oscillations. Methods. The well-known ordinary differential equations (ODE) integrator VODE was used to explore initial conditions and parameter space in a gas phase chemical model of a dark interstellar cloud. Results. We recall that the time evolution of the various chemical abundances under fixed temperature conditions depends on the density over cosmic ionization rate nH∕ζ ratio. We also report the occurrence of naturally sustained oscillations for a limited but well-defined range of control parameters. The period of oscillations is within the range of characteristic timescales of interstellar processes and could lead to spectacular resonances in time-dependent models. Reservoir species (C, CO, NH3,...) oscillation amplitudes are generally less than a factor two. However, these amplitudes reach a factor ten to thousand for low abundance species, e.g. HCN, ND3, that may play a key role for diagnostic purposes. The mechanism responsible for oscillations is tightly linked to the chemistry of nitrogen, and requires long chains of reactions such as found in multi-deuteration processes. [ABSTRACT FROM AUTHOR]

Context. Understanding the star-forming processes is key to understanding the evolution of galaxies. Investigating star formation requires precise knowledge of the properties of the dense molecular gas complexes where stars form and a quantification of how they are affected by the physical conditions to which they are exposed. The proximity, low metallicity, and wide range of star formation activity of the Large and Small Magellanic Clouds (LMC and SMC) make them prime laboratories to study how local physical conditions impact the dense gas reservoirs and their star formation efficiency. Aims. The aim of the Dense Gas Survey for the Magellanic Clouds (DeGaS-MC) project is to expand our knowledge of the relation between dense gas properties and star formation activity by targeting the LMC and SMC observed in the HCO+(2−1) and HCN(2−1) transitions. Methods. We carried out a pointing survey targeting two lines toward ∼30 LMC and SMC molecular clouds using the SEPIA180 instrument installed on the Atacama Pathfinder EXperiment (APEX) telescope. We performed a follow-up mapping campaign of the emission in the same transition in 13 star-forming regions. This first paper provides line characteristic catalogs and integrated line-intensity maps of the sources. Results. HCO+(2−1) is detected in 20 and HCN(2−1) in 8 of the 29 pointings observed. The dense gas velocity pattern follows the line-of-sight velocity field derived from the stellar population. The three SMC sources targeted during the mapping campaign were unfortunately not detected in our mapping campaign but both lines are detected toward the LMC 30Dor, N44, N105, N113, N159W, N159E, and N214 regions. The HCN emission is less extended than the HCO+ emission and is restricted to the densest regions. The HCO+(2−1)/HCN(2−1) brightness temperature ratios range from 1 to 7, which is consistent with the large ratios commonly observed in low-metallicity environments. A larger number of young stellar objects are found at high HCO+ intensities and lower HCO+/HCN flux ratios, and thus toward denser lines of sight. The dense gas luminosities correlate with the star formation rate traced by the total infrared luminosity over the two orders of magnitude covered by our observations, although substantial region-to-region variations are observed. [ABSTRACT FROM AUTHOR]

Context. The interaction between dust, ice, and gas during the formation of stars produces complex organic molecules. While observations indicate that several species are formed on ice-covered dust grains and are released into the gas phase, the exact chemical interplay between solid and gas phases and their relative importance remain unclear. Aims. Our goal is to study the interplay between dust, ice, and gas in regions of low-mass star formation through ice- and gas-mapping and by directly measuring gas-to-ice ratios. This provides constraints on the routes that lead to the chemical complexity that is observed in solid and gas phases. Methods. We present observations of gas-phase methanol (CH3OH) and carbon monoxide (13CO and C18O) at 1.3 mm towards ten low-mass young protostars in the Serpens SVS 4 cluster from the SubMillimeter Array (SMA) and the Atacama Pathfinder EXperiment (APEX) telescope. We used archival data from the Very Large Telescope (VLT) to derive abundances of ice H2O, CO, and CH3OH towards the same region. Finally, we constructed gas-ice maps of SVS 4 and directly measured CO and CH3OH gas-to-ice ratios. Results. The SVS 4 cluster is characterised by a global temperature of 15 ± 5 K. At this temperature, the chemical behaviours of CH3OH and CO are anti-correlated: larger variations are observed for CH3OH gas than for CH3OH ice, whereas the opposite is seen for CO. The gas-to-ice ratios (Ngas/Nice) range from 1–6 for CO and 1.4 × 10−4–3.7 × 10−3 for CH3OH. The CO gas-maps trace an extended gaseous component that is not sensitive to the effect of freeze-out. Because of temperature variations and dust heating around 20 K, the frozen CO is efficiently desorbed. The CH3OH gas-maps, in contrast, probe regions where methanol is predominantly formed and present in ices and is released into the gas phase through non-thermal desorption mechanisms. Conclusions. Combining gas- and ice-mapping techniques, we measure gas-to-ice ratios of CO and CH3OH in the SVS 4 cluster. The CH3OH gas-to-ice ratio agrees with values that were previously reported for embedded Class 0/I low-mass protostars. We find that there is no straightforward correlation between CO and CH3OH gas with their ice counterparts in the cluster. This is likely related to the complex morphology of SVS 4: the Class 0 protostar SMM 4 and its envelope lie in the vicinity, and the outflow associated with SMM 4 intersects the cluster. This study serves as a pathfinder for future observations with ALMA and the James Webb Space Telescope (JWST) that will provide high-sensitivity gas-ice maps of molecules more complex than methanol. Such comparative maps will be essential to constrain the chemical routes that regulate the chemical complexity in star-forming regions. [ABSTRACT FROM AUTHOR]

Context. The inclusion of molecular physics is an important piece that tends to be missing from the puzzle when modeling the spectra of supernovae (SNe). Molecules have both a direct impact on the spectra, particularly in the infrared, and an indirect one as a result of their influence on certain physical conditions, such as temperature. Aims. In this paper, we aim to investigate molecular formation and non-local thermodynamic equilibrium (NLTE) cooling, with a particular focus on CO, the most commonly detected molecule in supernovae. We also aim to determine the dependency of supernova chemistry on physical parameters and the relative sensitivity to rate uncertainties. Methods. We implemented a chemical kinetic description of the destruction and formation of molecules into the SN spectral synthesis code SUMO. In addition, selected molecules were coupled into the full NLTE level population framework and, thus, we incorporated molecular NLTE cooling into the temperature equation. We produced a test model of the CO formation in SN 1987A between 150 and 600 days and investigated the sensitivity of the resulting molecular masses to the input parameters. Results. We find that there is a close inter-dependency between the thermal evolution and the amount of CO formed, mainly through an important temperature-sensitive CO destruction process with O+. After a few hundred days, CO completely dominates the cooling of the oxygen-carbon zone of the supernova which, therefore, contributes little optical emission. The uncertainty of the calculated CO mass scales approximately linearly with the typical uncertainty factor for individual rates. We demonstrate how molecular masses can potentially be used to constrain various physical parameters of the supernova. [ABSTRACT FROM AUTHOR]

Context. The Rosetta spacecraft escorted Comet 67P/Churyumov-Gerasimenko for 2 yr along its journey through the Solar System between 3.8 and 1.24 au. Thanks to the high resolution mass spectrometer on board Rosetta, the detailed ion composition within a coma has been accurately assessed in situ for the very first time. Aims. Previous cometary missions, such as Giotto, did not have the instrumental capabilities to identify the exact nature of the plasma in a coma because the mass resolution of the spectrometers onboard was too low to separate ion species with similar masses. In contrast, the Double Focusing Mass Spectrometer (DFMS), part of the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis on board Rosetta (ROSINA), with its high mass resolution mode, outperformed all of them, revealing the diversity of cometary ions. Methods. We calibrated and analysed the set of spectra acquired by DFMS in ion mode from October 2014 to April 2016. In particular, we focused on the range from 13–39 u q−1. The high mass resolution of DFMS allows for accurate identifications of ions with quasi-similar masses, separating 13C+ from CH+, for instance. Results. We confirm the presence in situ of predicted cations at comets, such as CH m+ $_m^+$ m + (m = 1−4), HnO+ (n = 1−3), O+, Na+, and several ionised and protonated molecules. Prior to Rosetta, only a fraction of them had been confirmed from Earth-based observations. In addition, we report for the first time the unambiguous presence of a molecular dication in the gas envelope of a Solar System body, namely CO 2++ $_2^{++}$ 2 + + . [ABSTRACT FROM AUTHOR]

In this article, we simulated the collisions of an OH• projectile impacting on a methanol cluster formed by ten units of methanol to mimic an ice mantle (CH3OH)10. The chemical processes occurring after the impact were studied through Born-Oppenheimer (ab-initio) molecular dynamics. We focus on collisions with initial kinetic impact energy of 10–22 eV, where the richest chemistry happens. We report the formation mechanisms of stable complex organic molecules (COMs) such as methoxymethanol CH3OCH2OH, formic acid HCOOH, formyl radical HCO, formaldehyde H2CO and its elusive HCOH isomer. We show that CH2(OH)2, •CH2OH or +CH2OH are key intermediates to generate H2CO and other COMs. We compare the outcomes using OH• with those using OH− projectiles. These processes are likely relevant to the production of COMs in astrophysical environments. We discuss its formation mechanism and the astrophysical implications of these chemical pathways in star-forming regions. [ABSTRACT FROM AUTHOR]

In this article, we simulated the collisions of an OH• projectile impacting on a methanol cluster formed by ten units of methanol to mimic an ice mantle (CH3OH)10. The chemical processes occurring after the impact were studied through Born-Oppenheimer (ab-initio) molecular dynamics. We focus on collisions with initial kinetic impact energy of 10–22 eV, where the richest chemistry happens. We report the formation mechanisms of stable complex organic molecules (COMs) such as methoxymethanol CH3OCH2OH, formic acid HCOOH, formyl radical HCO, formaldehyde H2CO and its elusive HCOH isomer. We show that CH2(OH)2, •CH2OH or +CH2OH are key intermediates to generate H2CO and other COMs. We compare the outcomes using OH• with those using OH− projectiles. These processes are likely relevant to the production of COMs in astrophysical environments. We discuss its formation mechanism and the astrophysical implications of these chemical pathways in star-forming regions. [ABSTRACT FROM AUTHOR]

Context. Carbon fractionation has been studied from a theoretical point of view with different models of time-dependent chemistry, including both isotope-selective photodissociation and low-temperature isotopic exchange reactions. Aims. Recent chemical models predict that isotopic exchange reactions may lead to a depletion of 13C in nitrile-bearing species, with 12C/13C ratios two times higher than the elemental abundance ratio of 68 in the local interstellar medium. Since the carbon isotopic ratio is commonly used to evaluate the 14N/15N ratios with the double-isotope method, it is important to study carbon fractionation in detail to avoid incorrect assumptions. Methods. In this work, we implemented a gas-grain chemical model with new isotopic exchange reactions and investigated their introduction in the context of dense and cold molecular gas. In particular, we investigated the 12C/13C ratios of HNC, HCN, and CN using a grid of models, with temperatures and densities ranging from 10 to 50 K and 2 × 103 to 2 × 107 cm−3, respectively. Results. We suggest a possible 13C exchange through the 13C + C3 → 12C +13CC2 reaction, which does not result in dilution, but rather in 13C enhancement, for molecules that are formed starting from atomic carbon. This effect is efficient in a range of time between the formation of CO and its freeze-out on grains. Furthermore, the parameter-space exploration shows, on average, that the 12C/13C ratios of nitriles are predicted to be a factor 0.8–1.9 different from the local 12C/13C of 68 for high-mass star-forming regions. This result also affects the 14N/15N ratio: a value of 330 obtained with the double-isotope method is predicted to vary in the range 260–630, up to 1150, depending on the physical conditions. Finally, we studied the 12C/13C ratios of nitriles by varying the cosmic-ray ionisation rate, ζ: the 12C/13C ratios increase with ζ because of secondary photons and cosmic-ray reactions. [ABSTRACT FROM AUTHOR]

Context. Complex organic molecules (COMs) have been identified toward high- and low-mass protostars as well as molecular clouds, suggesting that these interstellar species originate from the early stage(s) of starformation. The reaction pathways resulting in COMs described by the formula C2HnO, such as acetaldehyde (CH3CHO), vinyl alcohol (CH2CHOH), ketene (CH2CO), and ethanol (CH3CH2OH), are still under debate. Several of these species have been detected in both translucent and dense clouds, where chemical processes are dominated by (ground-state) atom and radical surface reactions. Therefore, efficient formation pathways are needed to account for their appearance well before the so-called catastrophic CO freeze-out stage starts. Aims. In this work, we investigate the laboratory possible solid-state reactions that involve simple hydrocarbons and OH-radicals along with H2O ice under translucent cloud conditions (1 ≤ AV ≤ 5 and nH ~ 103 cm-3). We focus on the interactions of C2H2 with H-atoms and OH-radicals, which are produced along the H2O formation sequence on grain surfaces at 10 K. Methods. Ultra-high vacuum experiments were performed to study the surface chemistry observed during C2H2 + O2 + H codeposition, where O2 was used for the in situ generation of OH-radicals. These C2H2 experiments were extended by a set of similar experiments involving acetaldehyde (CH3CHO) - an abundant product of C2H2 + O2 + H codeposition. Reflection absorption infrared spectroscopy was applied to in situ monitor the initial and newly formed species. After that, a temperature-programmed desorption experiment combined with a quadrupole mass spectrometer was used as a complementary analytical tool. The IR and QMS spectral assignments were further confirmed in isotope labeling experiments using 18O2. Results. The investigated 10 K surface chemistry of C2H2 with H-atoms and OH-radicals not only results in semi and fully saturated hydrocarbons, such as ethylene (C2H4) and ethane (C2H6), but it also leads to the formation of COMs, such as vinyl alcohol, acetaldehyde, ketene, ethanol, and possibly acetic acid. It is concluded that OH-radical addition reactions to C2H2, acting as a molecular backbone, followed by isomerization (i.e., keto-enol tautomerization) via an intermolecular pathway and successive hydrogenation provides so far an experimentally unreported solid-state route for the formation of these species without the need of energetic input. The kinetics of acetaldehyde reacting with impacting H-atoms leading to ketene and ethanol is found to have a preference for the saturated product. The astronomical relevance of the reaction network introduced here is discussed. [ABSTRACT FROM AUTHOR]

Aims. We investigate the possible role of polycyclic aromatic hydrocarbons (PAHs) as a sink for deuterium in the interstellar medium (ISM) and study UV photolysis as a potential underlying chemical process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various isotopologs of deuterium-enriched, protonated anthracene and phenanthrene ions (both C14H10 isomers) was recorded in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. Infrared multiple photon dissociation spectroscopy using the Free-Electron Laser for Infrared eXperiments was applied to provide IR spectra. Infrared spectra calculated using density functional theory were compared to the experimental data to identify the isomers present in the experiment. Transition-state energies and reaction rates were also calculated and related to the experimentally observed fragmentation product abundances. Results. The photofragmentation mass spectra for both UV and IRMPD photolysis only show the loss of atomic hydrogen from [D-C14H10]+, whereas [H-C14D10]+ shows a strong preference for the elimination of deuterium. Transition state calculations reveal facile 1,2-H and -D shift reactions, with associated energy barriers lower than the energy supplied by the photo-excitation process. Together with confirmation of the ground-state structures via the IR spectra, we determined that the photolytic processes of the two different PAHs are largely governed by scrambling where the H and the D atoms relocate between different peripheral C atoms. The 0.1 eV difference in zero-point energy between C-H and C-D bonds ultimately leads to faster H scrambling than D scrambling, and increased H atom loss compared to D atom loss. Conclusions. We conclude that scrambling is common in PAH cations under UV radiation. Upon photoexcitation of deuteriumenriched PAHs, the scrambling results in a higher probability for the aliphatic D atom to migrate to a strongly bound aromatic site, protecting it from elimination. We speculate that this could lead to increased deuteration as a PAH moves towards more exposed interstellar environments. Also, large, compact PAHs with an aliphatic C-HD group on solo sites might be responsible for the majority of aliphatic C-D stretching bands seen in astronomical spectra. An accurate photochemical model of PAHs that considers deuterium scrambling is needed to study this further. [ABSTRACT FROM AUTHOR]

Context. The N2 and CO-rich and water-depleted comet C/2016 R2 (Pan-STARRS) - hereafter "C/2016 R2" - is a unique comet for detailed spectroscopic analysis. Aims. We aim to explore the associated photochemistry of parent species, which produces different metastable states and forbidden emissions, in this cometary coma of peculiar composition. Methods. We reanalyzed the high-resolution spectra of comet C/2016 R2 obtained in February 2018 using the UVES spectrograph of the European Southern Observatory Very Large Telescope. Various forbidden atomic emission lines of [CI], [NI], and [OI] were observed in the optical spectrum of this comet when it was at 2.8 au from the Sun. The observed forbidden emission intensity ratios are studied in the framework of a couple-chemistry emission model. Results. The model calculations show that CO2 is the major source of both atomic oxygen green and red doublet emissions in the coma of C/2016 R2 (while for most comets it is generally H2O), whereas, CO and N2 govern the atomic carbon and nitrogen emissions, respectively. Our modeled oxygen green-to-red-doublet and carbon-to-nitrogen emission ratios are higher by a factor of three than what is found from observations. These discrepancies could be due to uncertainties associated with photon cross sections or unknown production and/or loss sources. Our modeled oxygen green-to-red-doublet emission ratio is close to what is seen in observations when we consider an O2 abundance with a production rate of 30% relative to the CO production rate. We constrained the mean photodissociation yield of CO, producing C(1S) at about 1%, a quantity which has not been measured in the laboratory. The collisional quenching is not a significant loss process for N(2D) though its radiative lifetime is significant (~10 h). Hence, the observed [NI] doublet-emission ratio ([NI] 5198/5200) of 1.22, which is smaller than the terrestrial measurement by a factor 1.4, is mainly due to the characteristic radiative decay of N(2D). [ABSTRACT FROM AUTHOR]

Context. CO rovibrational lines are efficient probes of warm molecular gas and can give unique insights into the inner 10 AU of proto-planetary disks, effectively complementing ALMA observations. Recent studies find a relation between the ratio of lines originating from the second and first vibrationally excited state, denoted as v2∕v1, and the Keplerian velocity or emitting radius of CO. Counterintuitively, in disks around Herbig Ae stars the vibrational excitation is low when CO lines come from close to the star, and high when lines only probe gas at large radii (more than 5 AU). The v2∕v1 ratio is also counterintuitively anti-correlated with the near-infrared (NIR) excess, which probes hot and warm dust in the inner disk. Aims. We aim to find explanations for the observed trends between CO vibrational ratio, emitting radii and NIR excess, and to identify their implications in terms of the physical and chemical structure of inner disks around Herbig stars. Methods. First, slab model explorations in local thermal equilibrium (LTE) and non-LTE are used to identify the essential parameter space regions that can produce the observed CO emission. Second, we explore a grid of thermo-chemical models using the DALI code, varying gas-to-dust ratio and inner disk radius. Line flux, line ratios, and emitting radii are extracted from the simulated lines in the same way as the observations and directly compared to the data. Results. Broad CO lines with low vibrational ratios are best explained by a warm (400–1300 K) inner disk surface with gas-to-dust ratios below 1000 (NCO < 1018 cm−2); no CO is detected within or at the inner dust rim, due to dissociation at high temperatures. In contrast, explaining the narrow lines with high vibrational ratios requires an inner cavity of a least 5 AU in both dust and gas, followed by a cool (100–300 K) molecular gas reservoir with gas-to-dust ratios greater than 10 000 (NCO > 1018 cm−2) at the cavity wall. In all cases, the CO gas must be close to thermalization with the dust (Tgas ~ Tdust). Conclusions. The high gas-to-dust ratios needed to explain high v2∕v1 in narrow CO lines for a subset of group I disks can be naturally interpreted as due to the dust traps that are proposed to explain millimeter dust cavities. The dust trap and the low gas surface density inside the cavity are consistent with the presence of one or more massive planets. The difference between group I disks with low and high NIR excess can be explained by gap opening mechanisms that do or do not create an efficient dust trap, respectively. The broad lines seen in most group II objects indicate a very flat disk in addition to inner disk substructures within 10 AU that can be related to the substructures recently observed with ALMA. We provide simulated ELT-METIS images to directly test these scenarios in the future. [ABSTRACT FROM AUTHOR]

Context. As the fourth most abundant element in the universe, carbon (C) is widespread in the interstellar medium (ISM) in various allotropic forms (e.g. fullerenes have been identified unambiguously in many astronomical environments, the presence of polycyclic aromatic hydrocarbon molecules in space has been commonly acknowledged, and presolar graphite, as well as nanodiamonds, have been identified in meteorites). As stable allotropes of these species, whether carbon nanotubes (CNTs) and their hydrogenated counterparts are also present in the ISM or not is unknown. Aims. The aim of the present works is to explore the possible routes for the formation of CNTs in the ISM and calculate their fingerprint vibrational spectral features in the infrared (IR). Methods. We studied the hydrogen-abstraction and acetylene-addition (HACA) mechanism and investigated the synthesis of nanotubes using density functional theory (DFT). The IR vibrational spectra of CNTs and hydrogenated nanotubes (HNTs), as well as their cations, were obtained with DFT. Results. We find that CNTs could be synthesized in space through a feasible formation pathway. CNTs and cationic CNTs, as well as their hydrogenated counterparts, exhibit intense vibrational transitions in the IR. Their possible presence in the ISM could be investigated by comparing the calculated vibrational spectra with astronomical observations made by the Infrared Space Observatory, Spitzer Space Telescope, and particularly the upcoming James Webb Space Telescope. [ABSTRACT FROM AUTHOR]

Context. The study of noble gas compounds has gained renewed interest thanks to the recent detection of ArH+ in the interstellar medium (ISM). The analysis of physical-chemical conditions in the regions of the ISM where ArH+ is observed requires accurate collisional data of ArH+ with He, H2, electrons, and H. Aims. The main goals of this work are to compute the first three-dimensional potential energy surface (PES) to study the interaction of ArH+ with He, analyze the influence of the isotopic effects in the rate coefficients, and evaluate the rovibrational relaxation rates. Methods. Two ab initio grids of energy were computed at the coupled cluster with single, double, and perturbative triple excitations (CCSD(T)) level of theory using the augmented correlation consistent polarized quadruple, and quintuple zeta basis sets (aug-cc-pVQZ, and aug-cc-pV5Z) and a grid at the complete basis set limit was determined. The analytical representation of the PES was performed using the reproducing kernel Hilbert space (RKHS). The dynamics of the system was studied using the close coupling method. Results. The differences in the rate coefficients for the isotopes 36ArH+, 38ArH+, and 40ArH+ in collision with He are negligible. However, the rotational rates for the collision of ArD+ with He cannot be estimated from those for ArH++He. Comparison with previous rates for the 36ArH++He collision showed discrepancies for ∣ Δj ∣ > 2, and in the case of high initial rotational states of 36ArH+ differences were found even for ∣ Δj ∣ = 1. The rates for transitions between different vibrational states were also examined. Finally, new sets of rotational rates for 36ArH++He and 36ArD++He are reported. [ABSTRACT FROM AUTHOR]

Context. Because of their high reactivity, the CH and OH radicals are of particular interest in astrochemistry. Modeling of CH and OH molecules requires the calculation of accurate radiative Einstein coefficients and rate coefficients for (de)excitation by collisions with the most abundant species such as H2 and He. Aims. The present paper focuses on the calculation of inelastic rate coefficients among the lowest OH/CH hyperfine levels in their ground vibrational state induced by collisions with He atoms. Methods. Calculations of hyperfine (de)excitation of CH/OH by He were performed using the close-coupling and recoupling methods from the most recent ab initio potential energy surfaces. Results. Cross sections for transitions among the 60 and 56 lowest hyperfine levels of CH and OH, respectively, were calculated for collision energies up to 2500 cm−1. These cross-sections were used to calculate the rate coefficients for temperatures between 10 and 300 K. A propensity rule for transitions with ΔF = Δj was observed. Conclusions. The new rate coefficients will help significantly in interpreting the CH/OH spectroscopic data observed with current and future telescopes, and help to accurately describe the OH masers and the hyperfine anomalies in CH emission spectra. [ABSTRACT FROM AUTHOR]

Context. Magnetic fields in cool stars can be investigated by measuring Zeeman line broadening and polarization in atomic and molecular lines. Similar to the Sun, these fields are complex and height-dependent. Many molecular lines dominating M-dwarf spectra (e.g., FeH, CaH, MgH, and TiO) are temperature- and Zeeman-sensitive and form at different atmospheric heights, which makes them excellent probes of magnetic fields on M dwarfs. Aims. Our goal is to analyze the complexity of magnetic fields in M dwarfs. We investigate how magnetic fields vary with the stellar temperature and how "surface" inhomogeneities are distributed in height – the dimension that is usually neglected in stellar magnetic studies. Methods. We have determined effective temperatures of the photosphere and of magnetic features, magnetic field strengths and filling factors for nine M dwarfs (M1–M7). Our χ2 analysis is based on a comparison of observed and synthetic intensity and circular polarization profiles. Stokes profiles were calculated by solving polarized radiative transfer equations. Results. Properties of magnetic structures depend on the analyzed atomic or molecular species and their formation heights. Two types of magnetic features similar to those on the Sun have been found: a cooler (starspots) and a hotter (network) one. The magnetic field strength in both starspots and network is within 3–6 kG, on average it is 5 kG. These fields occupy a large fraction of M dwarf atmospheres at all heights, up to 100%. The plasma β is less than one, implying highly magnetized stars. Conclusions. A combination of molecular and atomic species and a simultaneous analysis of intensity and circular polarization spectra have allowed us to better decipher the complexity of magnetic fields on M dwarfs, including their dependence on the atmospheric height. This work provides an opportunity to investigate a larger sample of M dwarfs and L-type brown dwarfs. [ABSTRACT FROM AUTHOR]

Context. The extent of the gas in protoplanetary discs is observed to be universally larger than the extent of the dust. This is often attributed to radial drift and grain growth of the millimetre grains, but line optical depth produces a similar observational signature. Aims. We investigate in which parts of the disc structure parameter space dust evolution and line optical depth are the dominant drivers of the observed gas and dust size difference. Methods. Using the thermochemical model DALI with dust evolution included we ran a grid of models aimed at reproducing the observed gas and dust size dichotomy. Results. The relation between Rdust and dust evolution is non-monotonic and depends on the disc structure. The quantity Rgas is directly related to the radius where the CO column density drops below 1015 cm−2 and CO becomes photodissociated; Rgas is not affected by dust evolution but scales with the total CO content of the disc. While these cases are rare in current observations, Rgas/Rdust > 4 is a clear sign of dust evolution and radial drift in discs. For discs with a smaller Rgas/Rdust, identifying dust evolution from Rgas/Rdust requires modelling the disc structure including the total CO content. To minimize the uncertainties due to observational factors requires FWHMbeam < 1× the characteristic radius and a peak S/N > 10 on the 12CO emission moment zero map. For the dust outer radius to enclose most of the disc mass, it should be defined using a high fraction (90–95%) of the total flux. For the gas, any radius enclosing >60% of the 12CO flux contains most of the disc mass. Conclusions. To distinguish radial drift and grain growth from line optical depth effects based on size ratios requires discs to be observed at high enough angular resolution and the disc structure should to be modelled to account for the total CO content of the disc. [ABSTRACT FROM AUTHOR]