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The recent detection of CN-functionalized aromatics partly addresses the long-standing mystery of the apparent absence of five- and six-membered rings in interstellar environments. Nitrogen (N)-heterocycles, which are crucial as the fundamental structures of nucleobases, have been a focus of these aromatic searches due to their biological significance. Although N-heterocycles have not been conclusively detected in astrophysical environments, their presence in chondrites and meteorites signifies their interstellar and circumstellar connection. Precise spectral data identify the unique signatures of molecules, confirming their presence in space. In this light, this work reports an extensive computational investigation on interstellar 3-pyrroline, a five-membered ring N-heterocycle. This includes an alternative formation route in cold interstellar environments and highly accurate rotational and vibrational spectroscopy. The results indicate that 3-pyrroline can form on dust grain surfaces from vinyl cyanide, as its formation from pyrrole through double hydrogenation may lead to the formation of pyrrole itself via an H2-abstraction process. 3-Pyrroline's rotational transition at 52.3 GHz offers a potential tool for its detection in cold interstellar regions. Additionally, the strongest infrared (IR) features of 3-pyrroline at 16.09 and |$\sim$| 3.50 |$\mu$| m are observable with JWST. The provided data are crucial for laboratory identification and future interstellar observations of 3-pyrroline at both radio and IR wavelengths. [ABSTRACT FROM AUTHOR]

Aminoacetonitrile (AAN), also known as glycinenitrile, has been suggested as a possible precursor of glycine and adenine in the interstellar medium. Here, we present the chemical modelling of AAN and its isomers in hot cores using the three-phase chemical model NAUTILUS with the addition of over 300 chemical reactions of the three AAN isomers and related species. Our models predicted a peak gas-phase abundance of AAN reaching the order of 10 |$^{-8}$|⁠ , which is consistent with observation towards Sgr B2(N). Regarding the reaction pathways of AAN and its isomers, we found that AAN is primarily formed via free radical reactions on grain surfaces during the early evolutionary stages. Subsequently, it is thermally desorbed into the gas phase as the temperature rises and is then destroyed by positive ions and radicals in gas phase. The isomers of AAN are formed through the hydrogenation reaction of CH |$_3$| NCN on the grain surface and via electron recombination reactions of ion C |$_2$| H |$_5$| N |$_2^+$| in gas phase. We speculate that there is a possibility for NCCN and AAN to react with each other, eventually leading to the formation of adenine in hot cores. However, further investigation is required to understand the efficiency of grain surfaces in adenine formation, through theoretical calculations or laboratory experiments in future research. [ABSTRACT FROM AUTHOR]

Cross-sections and rate coefficients for the radiative association processes of Al(2P) with Cl(2P) for the formation of aluminium monochloride (AlCl) and P+(3P) with Cl(2P) to form phosphorus monochloryl cation (PCl+) have been estimated as a function of temperature. Rate coefficients have been estimated from cross-sections, which are calculated using a quantum mechanical method. They are found to vary from 4.95 × 10–21 to 4.24 × 10–16 and from 7.10 × 10–18 to 3.50 × 10–17 cm3 s–1 for AlCl and PCl+, respectively, for temperatures ranging from 10 to 15   000 K. The obtained rate constants are fitted with the Arrhenius–Kooij functions for incorporation into astrochemical reaction data bases. [ABSTRACT FROM AUTHOR]

Detection of the AlCl molecule in IRC+10216 has been reported in the literature. We here report calculations of reaction rate constants for formation of AlCl through radiative association of Al and Cl for a temperature interval of 1000 to 14000 K. Potential energy and permanent/transition dipole moment curves were taken from the literature. Quantum mechanical and semiclassical/classical methods were used to obtain the reaction cross-sections and thermal rate constants, accounting for shape resonances with Breit–Wigner theory. Both the A |$^1 \Pi \rightarrow$| X |$^1 \Sigma ^+$| transition and the X |$^1 \Sigma ^+\rightarrow$| X |$^1 \Sigma ^+$| transition have been treated, with results showing that the former dominates for the temperatures considered in this study. Our rate constants are a factor of two to three larger than previously calculated values, where the latter were obtained without considering resonances or the X |$^1 \Sigma ^+\rightarrow$| X |$^1 \Sigma ^+$| transition. Our new values do however not change the previous conclusion that radiative association can only contribute modestly to the formation of AlCl under the given conditions. [ABSTRACT FROM AUTHOR]

Forsterite is a primary constituent of interstellar dust and planetary systems. It is believed to originate from the outflows of oxygen-rich stars and undergo further processing within the interstellar medium through the action of cosmic rays and shocks. Under these harsh conditions, point defects may form, such as MgO Schottky vacancies. These vacancies can then undergo atom reconstruction as part of a chemical process to maintain the system's crystalline structure. Polycyclic aromatic hydrocarbons (PAHs) are ubiquitously observed interstellar molecules and are thought to form through gas-phase reactions akin to sooting flames. However, their role and impact on dust stability remain unknown. In this study, we employ an atomistic artificial-intelligence-based method, surrogate machine learning trained directly by density functional theory. Specifically, we utilize gofee (global optimization with first-principles energy expressions) to predict possible reconstructions of MgO vacancies on a crystalline forsterite (010) surface as an important component of interstellar dust and planetary systems. We identify nine possible reconstructions involving the formation of unbound Si and O atoms. We investigate their energy stability and find that the reconstruction of Si–O atoms stabilizes the vacancy by about 0.54 eV. Additionally, if PAHs bind with the unbound O and Si atoms of the vacancy, the vacancy is stabilized by approximately 1.76 eV. We demonstrate that PAHs, along with the reconstruction of unbound atoms on the dust surface, affect the stability of the dust, which might open up avenues for diverse chemistry. [ABSTRACT FROM AUTHOR]

In this study, we use the UK Molecular r-matrix (ukrmol) codes in the close-coupling approximation to examine the photoionization of hydrogen halides (hydrogen fluoride, hydrogen chloride, and hydrogen bromide). This article reports the total and partial photoionization cross-sections for the |$\mathrm{X}^2 \Pi$|⁠ , |$\mathrm{A}^2 \Sigma ^{+}$|⁠ , and |$\mathrm{B}^2 \Sigma ^{+}$| ionic states of these halides. The calculated cross-sections are compared with the available literature, which does not accurately represent the effective cross-sections near the threshold region, which is dominated by the Rydberg series autoionization resonances converging to the |$\mathrm{A}^2 \Sigma ^{+}$| ionic state. There seems to have been minimal effort to investigate the Rydberg-bound states of these halides. Meanwhile, the r-matrix approaches have traditionally excelled at characterizing such studies. This indicates the effectiveness of this method for molecular photoionization as well as for understanding the resonant contribution to the photoionization cross-sections. The detailed cross-sections calculated comprise the complex autoionizing resonance structures capable of significantly contributing to the computations of total photoionization rates, which are necessary to maintain a steady state of ionization in astrophysical plasmas. Comparisons with the experimental measurements and the theoretical data generally show reasonable agreement across the reported energy range. [ABSTRACT FROM AUTHOR]

In comets and in the cold phase of the interstellar medium (ISM), ammonium salts are key molecular species due to their role in the retention of volatile compounds on cold surfaces. In the case of sulphur, the H |$_2$| S/OCS ratio observed in protostars could be explained by the presence of ammonium hydrosulphide (NH |$_4$| SH) salts. However, laboratory data on the properties of NH4SH in ISM cold relevant conditions are rather scarce, as they usually focus on the atmosphere of Jupiter. We propose to consolidate the laboratory data regarding NH |$_4$| SH on grains, by performing temperature programmed desorption experiments and Fourier transform infrared reflection spectroscopy. The salt was also exposed to H atoms to mimic the ISM conditions. NH |$_4$| SH was found to form in situ at 10 K, from a mixture of ammonia (NH |$_3$|⁠) and hydrogen sulphide (H |$_2$| S). The NH |$_4^+$| infrared feature (1485 cm |$^{-1}$|⁠) is the most prominent one at 80 K. As pure species, H |$_2$| S and NH |$_3$| desorb at 76 and 90 K, respectively, whereas they are released into the gas phase at 153 K when adsorbed in the form of salt. The presence of water delays the desorption of the salt until the very end of the water desorption, but does not affect the desorption kinetics. During H-exposure, the salt is dissociated and no new product was detected. As a comparative study, salts have been included in the Nautilus gas–grain model. The results show a good correlation with the observations of IRAS 16293−2422B, as opposed to when NH |$_4$| SH is not included in the model. [ABSTRACT FROM AUTHOR]

In this work, the gas-phase ion–atom collision reaction between large cationic carbon clusters and H-atoms is investigated. The carbon cluster cations (C |$_{48-2*n}$| |$^+$|⁠ , n = [0 |$-$| 8]) are produced from the photo-fragmentation processes of large PAH (dicoronylene, DC, C |$_{48}$| H |$_{20}$|⁠) cations. The hydrogenated carbon cluster cations are efficiently formed (e.g. C |$_{44/46}$| H |$_{9}$| |$^+$|⁠), and no even–odd hydrogenated mass patterns are observed. The hydrogenation behaviour and hydrogenation rate for these carbon cluster cations are the same. With theoretical calculations, the formation and bending processes of carbon cluster cations, the structure of these newly formed hydrogenated carbon cluster cations, and the bonding energies for the hydrogenation pathways are investigated. During the formation process of carbon clusters, the zigzagged edges gradually increase, and the planar configuration tends towards a bent and folded molecular configuration, i.e. from graphene to fullerene structures. The bending process with higher exothermic energies provides a reasonable explanation for the formation of the 'magic numbers' (e.g. C-atoms = 44) carbon clusters and their greater stability. The exothermic energy for each hydrogenation reaction pathway is relatively high; consequently, the forms and the hydrogenated states of carbon clusters are complex. The hydrogenation ability of edge carbon sites is higher than that of internal carbon sites; after bending and folding, the hydrogenation ability of these originally internal carbon sites becomes higher due to structural caged. As a result, under the co-evolution interstellar chemistry network, the (hydrogenation) states and forms of carbon compounds are complicated and diverse in the ISM. [ABSTRACT FROM AUTHOR]

For a better understanding of the physico-chemistry in the interstellar medium, collisional data are needed. In this work, we provide rate coefficients for the recently detected by Cabezas and collaborators in 2023 sodium cyanoacetylide molecule NaC |$_{3}$| N(⁠|$X^{1}\Sigma ^{+}$|⁠) induced by collisions with He. A new two-dimensional potential energy surface (2D-PES) is derived by adopting the high-level theory of the explicitly correlated coupled cluster with single, double, and perturbative triple excitations (CCSD(T)-F12) in conjunction with the aug-cc-pVTZ basis sets. Our 2D-PES presents two minima: the global one with a well depth of |$-86.58$|  cm |$^{-1}$| and the second well with a |$-47.01$|  cm |$^{-1}$| depth. This was expected by the Natural Bond Orbital analysis showing two electrophilic zones located on Na and N linked Carbon with respective atomic charges : |$+0.96575$| and |$+0.28910$|⁠. This PES was used to calculate inelastic cross-sections within the framework of the close-coupling theory for total energies |$\le 170$|  cm |$^{-1}$| and |$J\le 22$|⁠. Using the Maxwell–Boltzmann distribution of kinetic energies, these cross-sections were integrated to generate the collisional (de)-excitation rate coefficients for temperatures below 30 K. In order to estimate the impact of the computed collisional rates, a non-local thermodynamical equilibrium radiative transfer calculation was performed. The new collisional data can allow accurate NaC |$_{3}$| N abundance determination in the interstellar medium. [ABSTRACT FROM AUTHOR]

The nearby oxygen-rich AGB star L |$_2$|  Pup hosts a well-studied nearly edge-on disc. To date, discs around AGB stars have not been chemically studied in detail. By combining a parametrization commonly used for protoplanetary discs and archival ALMA observations, we retrieved an updated density and temperature structure of this disc. This physical model was then used as input to the first chemical model of an AGB disc. The model shows that the physical structure of the disc has a large impact on its chemistry, with certain species showing large changes in column density relative to a radial outflow, indicating that chemistry could be used as a tracer of discs that cannot be directly imaged. Despite its oxygen-rich nature, the daughter species formed within the disc are surprisingly carbon-rich. Two chemical regimes can be distinguished: cosmic-ray induced chemistry in the midplane and photochemistry induced by the interstellar radiation field in the outer regions. Certain complex organic molecules are formed in the midplane. This occurs via gas-phase chemistry only, as the disc is too warm for dust-gas chemistry. The photochemistry in the outer regions leads to the efficient formation of (long) carbon-chains. The predictions of the model allow us to tentatively put the disc's age |$\lesssim 10^5$| yr. Additional observations are necessary to better constrain the physical structure of L |$_2$|  Pup's disc and are essential to test the predictions made by the chemical model. Our exploratory work paves the way for a more general study of the chemistry of AGB discs. [ABSTRACT FROM AUTHOR]

Carbon monoxide (CO) emission has been observed in a number of core-collapse supernovae (SNe) and is known to be an important coolant at late times. We have implemented a chemical reaction network in the radiative-transfer code cmfgen to investigate the formation of CO and its impact on SN ejecta. We calculate two 1D SN models with and without CO: a BSG explosion model at one nebular epoch and a full time-sequence (50–300 d) for a red supergiant explosion. In both models, CO forms at nebular times in the dense, inner regions at velocities <2000 km s |$^{-1}$|  where line emission from CO can dominate the cooling and reduce the local temperature by as much as a factor of 2, weakening emission lines and causing the optical light curve to fade faster. That energy is instead emitted in CO bands, primarily the fundamental band at |$\sim 4.5 \mathrm{\mu m}$|⁠ , which accounts for up to 20 per cent of the total luminosity at late times. However, the non-monotonic nature of the CO cooling function can cause numerical difficulties and introduce multiple temperature solutions. This issue is compounded by the sensitivity of the CO abundance to a few reaction rates, many of which have large uncertainties or disparate values across literature sources. Our results also suggest that, in many SNe, CO-level populations are far from their local thermodynamic equilibrium values. Unfortunately, accurate collisional data, necessary to compute non-local thermodynamic equilibrium populations, are limited to a few transitions. [ABSTRACT FROM AUTHOR]

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]

We have critically reviewed the literature pertaining to reactions that are significant for the chemistry of hydrogen-, deuterium-, and helium-bearing species in the homogeneous early Universe. For each reaction rate coefficient, we provide a fit in the modified-Arrhenius form, specifying the corresponding uncertainty and temperature range. This new network, limited to 21 reactions, should be the most reliable to date. Combined with accurate state-to-state rate coefficients for inelastic and reactive collisions involving H2 and HD, it allows us for the first time to follow the evolution of the abundances of atomic and molecular species, level populations of H2 and HD, and the ortho:para ratio (OPR) of H2, in a self-consistent fashion during the adiabatic expansion of the universe. The abundances of H2 and HD change only marginally compared to previous models, indicating that the uncertainties on the main reaction rate coefficients have essentially been removed. We also find that the adiabatic expansion has a dramatic effect on the OPR of H2, which freezes-out at redshifts z ≲ 50. In contrast, at higher redshifts, the populations of the rotational levels of H2 and HD are predicted to be fully thermalized at the temperature of the cosmic background radiation field, a result that conflicts with some recent, independent calculations. This new network allows the chemistry of primordial gas to be followed during the early phase of collapse towards Population III star progenitors. [ABSTRACT FROM AUTHOR]

Despite hydrogen sulphide (H2S) has been predicted to be the major reservoir of S-bearing species on the icy mantles of interstellar grains, no solid H2S has been detected so far. A crucial parameter that governs whether or not a species remains frozen on to the grain mantles is its binding energy (BE). We present a new computational study of the H2S BE on a large amorphous water ice surface, constituted by 200 water molecules. The resulting H2S BE distribution ranges from 57 K (0.5 kJ mol−1) to 2406 K (20.0 kJ mol−1), with the average μ = 984 K (8.2 kJ mol−1). We discuss the reasons why the low bound of the newly computed BE distribution, which testifies to the very weak interaction of H2S with the ice surface, has never been found by previous theoretical or experimental works before. In addition, the low H2S BEs may also explain why frozen H2S is not detected in interstellar ices. Following previous molecular dynamics studies that show that the energy of reactions occurring on ice surfaces is quickly absorbed by the water molecules of the ice and conservatively assuming that 10 per cent of the HS + H → H2S formation energy (−369.5 kJ mol−1) is left to the newly formed H2S, its energy is more than twice the largest BE and five times the average BE and, hence, H2S will most likely leave the water surface. [ABSTRACT FROM AUTHOR]

In interstellar environment, fullerene species readily react with large molecules (e.g. polycyclic aromatic hydrocarbons, PAHs and their derivatives) in the gas phase, which may be the formation route of carbon dust grains in space. In this work, the gas-phase ion–molecule collision reaction between fullerene cations (⁠|${\rm C}_{n}\, ^+$|⁠ , n  = 32, 34,..., 60) and functionalized PAH molecules (9-hydroxyfluorene, C13H10O) are investigated both experimentally and theoretically. The experimental results show that fullerene/9-hydroxyfluorene cluster cations are efficiently formed, leading to a series of large fullerene/9-hydroxyfluorene cluster cations (e.g. [(C13H10O)C60]+, [(C13H10O)3C58]+, and [(C26H18O)(C13H10O)2C48]+). The binding energies and optimized structures of typical fullerene/9-hydroxyfluorene cluster cations were calculated. The bonding ability plays a decisive role in the cluster formation processes. The reaction surfaces, modes, and combination reaction sites can result in different binding energies, which represent the relative chemical reactivity. Therefore, the geometry and composition of fullerene/9-hydroxyfluorene cluster cations are complicated. In addition, there is an enhanced chemical reactivity for smaller fullerene cations, which is mainly attributed to the newly formed deformed carbon rings (e.g. 7 C-ring). As part of the co-evolution network of interstellar fullerene chemistry, our results suggest that ion–molecule collision reactions contribute to the formation of various fullerene/9-hydroxyfluorene cluster cations in the interstellar medium, providing insights into different chemical reactivity caused by oxygenated functional groups (e.g. hydroxyl, OH, or ether, C-O-C) on the cluster formations. [ABSTRACT FROM AUTHOR]

Recent years have seen excellent progress in modelling the entrainment of T ∼ 104 K atomic gas in galactic winds. However, the entrainment of cool, dusty T ∼ 10–100 K molecular gas, which is also observed outflowing at high velocity, is much less understood. Such gas, which can be 105 times denser than the hot wind, appears extremely difficult to entrain. We run 3D wind-tunnel simulations with photoionization self-shielding and evolve thermal dust sputtering and growth. Unlike almost all such simulations to date, we do not enforce any artificial temperature floor. We find efficient molecular gas formation and entrainment, as well as dust survival and growth through accretion. Key to this success is the formation of large amounts of 104 K atomic gas via mixing, which acts as a protective 'bubble wrap' and reduces the cloud overdensity to χ ∼ 100. This can be understood from the ratio of the mixing to cooling time. Before entrainment, when shear is large, t mix/ t cool ≲ 1, and gas cannot cool below the 'cooling bottleneck' at 5000 K. Thus, the cloud survival criterion is identical to the well-studied purely atomic case. After entrainment, when shear falls, t mix/ t cool > 1, and the cloud becomes multiphase, with comparable molecular and atomic masses. The broad temperature PDF, with abundant gas in the formally unstable |$50 \, {\rm K} \lt T \lt 5000 \, {\rm K}$| range, agrees with previous ISM simulations with driven turbulence and radiative cooling. Our findings have implications for dusty molecular gas in stellar and active galactic nuclei outflows, cluster filaments, 'jellyfish' galaxies, and asymptomatic giant branch winds. [ABSTRACT FROM AUTHOR]

To investigate the gas-phase hydrogenation processes of large, astronomically relevant cationic polycyclic aromatic hydrocarbon (PAH) molecules under the interstellar environments, the ion–molecule collision reaction between six PAH cations and H-atoms is studied. The experimental results show that the hydrogenated PAH cations are efficiently formed, and no even–odd hydrogenated mass patterns are observed in the hydrogenation processes. The structure of newly formed hydrogenated PAH cations and the bonding energy for the hydrogenation reaction pathways are investigated with quantum theoretical calculations. The exothermic energy for each reaction pathway is relatively high, and the competition between hydrogenation and dehydrogenation is confirmed. From the theoretical calculation, the bonding ability plays an important role in the gas-phase hydrogenation processes. The factors that affect the hydrogenation chemical reactivity are discussed, including the effect of carbon skeleton structure, the side-edged structure, the molecular size, the five- and six-membered C-ring structure, the bay region structure, and the neighbouring hydrogenation. The infrared spectra of hydrogenated PAH cations are also calculated. These results we obtain once again validate the complexity of hydrogenated PAH molecules, and provide the direction for the simulations and observations under the co-evolution interstellar chemistry network. We infer that if we do not consider other chemical evolution processes (e.g. photoevolution), then the hydrogenation states and forms of PAH compounds are intricate and complex in the interstellar medium. [ABSTRACT FROM AUTHOR]

The chemistry of H2O, CO, and other small molecular species in an isolated pre-stellar core, L1544, has been assessed in the context of a comprehensive gas-grain chemical model, coupled to an empirically constrained physical/dynamical model. Our main findings are (i) that the chemical network remains in near equilibrium as the core evolves towards star formation and the molecular abundances change in response to the evolving physical conditions. The gas-phase abundances at any time can be calculated accurately with equilibrium chemistry, and the concept of chemical clocks is meaningless in molecular clouds with similar conditions and dynamical time-scales, and (ii) A comparison of the results of complex and simple chemical networks indicates that the abundances of the dominant oxygen and carbon species, H2O, CO, C, and C+ are reasonably approximated by simple networks. In chemical equilibrium, the time-dependent differential terms vanish, and a simple network reduces to a few algebraic equations. This allows rapid calculation of the abundances most responsible for spectral line radiative cooling in molecular clouds with long dynamical time-scales. The dust ice mantles are highly structured and the ice layers retain a memory of the gas-phase abundances at the time of their deposition. A complex (gas-phase and gas-grain) chemical structure therefore exists, with cosmic-ray induced processes dominating in the inner regions. The inferred H2O abundance profiles for L1544 require that the outer parts of the core and also any medium exterior to the core are essentially transparent to the interstellar radiation field. [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]

To probe the physical conditions in molecular clouds, observations of the rotational transitions of a molecular system are very important. Thus, accurate modelling of the emission spectra of silicon carbides requires the calculation of collision rate coefficients for its systems. We determine here, the collisional rate coefficients for the excitation of SiC4 by He using a new potential energy surface. The state-to-state rate coefficients between the lower levels (j ≤ 28) are calculated using the coupled-channel and coupled-state methods for temperatures ranging from 5 to 300 K. Finally, we model the excitation of the SiC4 radical in cold molecular clouds and star-forming regions using a radiative transfer model. For this purpose, the new rate coefficients are used to estimate the molecular abundances in interstellar clouds. Therefore, we recommend the use of this new data set in any astrophysical model of SiC4 radical excitation. [ABSTRACT FROM AUTHOR]

We have computed cross-sections for elastic and inelastic scattering of electrons on small grains at low-collision energies. Significant differences are again found between the results obtained in the presence and the absence of a 'permanent' grain dipole moment. In addition to spherical grains, scattering on ellipsoidal grains is investigated. We conclude that the rate of electron attachment to interstellar grains may be substantially lower in regions of molecular clouds from which the radiation field is excluded, and where the grains are less likely to possess a dipole moment. [ABSTRACT FROM AUTHOR]

Determining physical conditions in interstellar environments requires reliable estimation of collisional data for molecules detected in space. In this work, we report a rate coefficients calculation of MgC3N(X 2Σ+) induced by collision with He. This study is based on a new 2D potential energy surface (2D-PES), obtained from the explicitly correlated restricted open-shell coupled cluster approach with single, double, and perturbative triple excitation (rccsd(t)-f12) and the aug-cc-pVTZ basis sets. The MgC3N–He PES presents a global minimum with a well depth of −45.6 cm−1. Based on this interaction potential, we derived the excitation cross-sections using the close-coupling quantum time-independent formalism for total energies ≤500 cm−1 and N ≤ 40. These cross-sections were then integrated on a Maxwell–Boltzmann distribution of kinetic energies to obtain the collisional (de)-excitation rate coefficients for thermal temperature below 100 K. A non-LTE radiative transfer calculation was performed using the present collisional rates in order to estimate their impact on the abundance of MgC3N. These collisional data can help astronomers for the detection and an accurate determination of MgC3N abundance in the investigated interstellar clouds. [ABSTRACT FROM AUTHOR]

Carbon monoxide (CO) plays a vital role in interstellar chemistry, existing abundantly in both gaseous and frozen environments. Understanding the radiation-driven chemistry of CO-rich ices is crucial for comprehending the formation and desorption of C-bearing molecules in the interstellar medium (ISM), particularly considering the potential impact of temperature on these processes. We report experimental data on irradiation processing of pure CO ice by cosmic ray analogues (95.2 MeV 136Xe23+ ions) at temperatures of 10, 15, and 20 K, in the IGLIAS set-up coupled to the IRRSUD beamline at GANIL (Caen, France). The evolution of the irradiated frozen samples was monitored by infrared spectroscopy. The computational PROCODA code allows us to quantify the chemical evolution of the samples, determining effective reaction rates coefficients (ERCs), molecular abundances at the chemical equilibrium (CE) phase, and desorption processes. The model integrated 18 chemical species – 8 observed (CO, CO2, C3, O3, C2O, C3O, C3O2, and C5O3) and 10 non-observed but predicted (C, O, C2, O2, CO3, C4O, C5O, C2O2, C2O3, C4O2) – linked via 156 reactions. Our findings reveal temperature-driven influences on molecular abundances at chemical equilibrium, desorption yields and rates, and ERC values. Certain reaction routes exhibit distinct thermochemical behaviours of gas- and ice-phase reactions which may be attributed to the presence of neighbouring molecules within the ice matrix. This study provides pivotal insights into the chemical evolution of CO-enriched ice under irradiation, impacting solid-state astrochemistry, clarifying molecular abundances, and advancing our understanding of ISM chemistry and temperature effects on ionized radiation-processed frozen ices. [ABSTRACT FROM AUTHOR]

We report elastic and inelastic cross-sections for fast superthermal 12C(3 P) and 13C(3 P) atoms scattering on 12CO2. The cross-sections were computed using quantum-mechanical rotationally close-coupling formalism with the electronic interaction described by a newly constructed potential energy surface correlating to the lowest energy asymptote of the complex. State-to-state rotational cross-sections, differential cross-sections, and derived transport properties of interest for energy relaxation are also reported. The computed elastic differential cross-sections are found to be strongly anisotropic, show significant energy dependence, and differ by up to 2 percent between the two isotopes of carbon. [ABSTRACT FROM AUTHOR]

In this work, we study deuterium fractionation in four starless cores in the low-mass star-forming region L1688 in the Ophiuchus molecular cloud. We study how the deuterium fraction (RD) changes with environment, compare deuteration of ions and neutrals, core centre and its envelope, and attempt to reproduce the observed results with a gas–grain chemical model. We chose high and low gas density tracers to study both core centre and the envelope. With the IRAM 30 m antenna, we mapped N2H+(1–0), N2D+(1–0), H13CO+ (1–0) and (2–1), DCO+(2–1), and p -NH2D(111–101) towards the chosen cores. The missing p -NH3 and N2H+(1–0) data were taken from the literature. To measure the molecular hydrogen column density, dust and gas temperature within the cores, we used the Herschel/SPIRE dust continuum emission data, the Green Bank Ammonia Survey data (NH3), and the COMPLETE survey data to estimate the upper limit on CO depletion. We present the deuterium fraction maps for three species towards four starless cores. Deuterium fraction of the core envelopes traced by DCO+/H13CO+ is one order of magnitude lower (∼0.08) than that of the core central parts traced by the nitrogen-bearing species (∼0.5). Deuterium fraction increases with the gas density as indicated by high deuterium fraction of high gas density tracers and low deuterium fraction of lower gas density tracers and by the decrease of RD with core radii, consistent with the predictions of the chemical model. Our model results show a good agreement with observations for RD (N2D+/N2H+) and R D (DCO+/HCO+) and underestimate the RD (NH2D/NH3). [ABSTRACT FROM AUTHOR]

The astrochemically relevant reactions of [H, C, N, S] isomers were studied both theoretically and experimentally. The energetics and barriers of H-atom-addition and H-atom-abstraction reactions were computed. Experimentally, [H, C, N, S] isomers were generated via in situ photolysis in a solid para -H2 matrix. The H-atom reaction and the photochemistry of these species were monitored by infrared spectroscopy. In the case of HNCS, the formation of HNCSH was observed. Tentatively two different conformers, syn,trans - and anti,trans -HNCSH, were identified. The subsequent H-atom-addition and H-atom-abstraction reactions did not effectively induce the isomerization of HNCS to HSCN. In the case of HCNS, the observation of the HCN product indirectly reveals H-atom addition to the S atom of HCNS, which is followed by the rupture of the N−S bond. While not explored experimentally, theoretical computations reveal negligible barrier heights for the H-atom-abstraction reactions of HSCN and HSNC. Therefore, H atoms might deplete these species in the interstellar medium (ISM). In contrast to the H-atom reactions, ultraviolet (UV) irradiation between 255 and 240 nm effectively isomerized the HNCS to HSCN and HSNC. Besides decomposition, HCNS isomerize to HNCS, HSCN, and HSNC upon exposure to UV radiation between 300 and 216 nm. In certain H-atom-free conditions, HSNC, not yet observed in the ISM, could potentially coexist in observable amounts with the already detected HNCS and HSCN in the ISM. Conversely, HCNS, another unidentified isomer in the ISM, is unlikely to accumulate there under UV radiation or in the presence of reactive radicals, including H atoms. [ABSTRACT FROM AUTHOR]

Sulphur depletion in the interstellar medium (ISM) is a long-standing issue, as only 1 per cent of its cosmic abundance is detected in dense molecular clouds (MCs), while it does not appear to be depleted in other environments. In addition to gas phase species, MCs also contain interstellar dust grains, which are irregular, micron-sized, solid aggregates of carbonaceous materials, and/or silicates. Grains provide a surface where species can meet, accrete, and react. Although freeze-out of sulphur on to dust grains could explain its depletion, only OCS and, tentatively, SO2 were observed on their surfaces. Therefore, it is our aim to investigate the interaction between sulphur-containing species and the exposed mineral core of the grains at a stage prior to when sulphur depletion is observed. Here, the grain core is represented by olivine nanoclusters, one of the most abundant minerals in the ISM, with composition Mg4Si2O8 and Mg3FeSi2O8. We performed a series of quantum mechanical calculations to characterize the adsorption of nine S-bearing species, both neutral and charged, on to the nanoclusters. Our calculations reveal that the Fe–S interaction is preferred to Mg–S, causing sometimes the chemisorption of the adsorbate. These species are more strongly adsorbed on the bare dust grain silicate cores than on water ice mantles, and hence therefore likely sticking on the surface of grains forming part of the grain core. This demonstrates that the interaction of bare grains with sulphur species in cloud envelopes can determine the S-depletion observed in dense molecular clouds. [ABSTRACT FROM AUTHOR]

The effect of para -hydrogen (j p = 0) collisions on the rotational de-excitation transitions of molecule NCCP is investigated in this study. The scattering information is obtained by spherically averaging a four-dimensional potential energy surface (4DPES) over various H2 molecule orientations. The calculations used the CCSD(T)-F12a method and aug-cc-pVTZ basis set to generate a 4DPES for the NCCP–H2 van der Waals system. Within the NCCP– para -H2 4DPES, a minimum energy point of 191.82 cm−1 is attained at a distance of 3.6 Å from the centre of mass of H2 and NCCP. To compute cross-sectional data for NCCP interacting with para -H2 (j p = 0), close coupling calculations are employed, encompassing total energies up to 600 cm−1. The resulting rate coefficients [ |$k_{j{\rightarrow }j^{\prime }}(T$|⁠)] are calculated across a temperature range spanning from 5 K to 200 K. In accordance with propensity, even Δ j = −2 transitions are highly preferred. Comparatively, the derived |$k_{j{\rightarrow }j^{\prime }}(T$|⁠) for NCCP–H2 are determined to be 1.5–4.5 times of NCCP–He. This observation implies that relying on a scaling factor of 1.38 to extrapolate rate coefficients for H2 collisions from those of NCCP–He is not a reliable approach. [ABSTRACT FROM AUTHOR]

N-heterocycles are of special relevance in astrobiology but at present no nitrogen-containing heterocycles have been detected in the interstellar medium (ISM). Thus far, the simplest N-heterocyclic compound, 2H-Azirine (c-C2H3N), has not been conclusively identified, despite being searched for. Recently, several cyano and ethynyl derivatives of unsaturated hydrocarbons have been discovered in the cold prestellar core Taurus Molecular Cloud 1 (TMC-1). The purpose of this work is to assess the feasibility of the possible formation of cyano and ethynyl derivatives of azirine (c-C2H2N-CN, c-C2H2N-CCH) under interstellar conditions and provide high-level theoretical spectroscopic parameters of the most relevant cyano- and ethynyl-azirine isomers to facilitate their experimental identification. Six isomers are located for each, cyano- and ethynyl-azirine derivatives, and their interconversion processes are studied. The reactions of 2H-azirine with the CN or CCH radicals in the gas phase are explored as possible formation routes of cyano and ethynyl azirine. We found that the formation processes of the most stable isomers, namely 3-cyano-2H-azirine, 2-cyano-2H-azirine, 3-ethynyl-2H-azirine, and 2-ethynyl-2H-azirine, are exothermic and barrier free. Thus, these compounds stand out as potential targets to be searched for in space. Based on the newly determined rotational spectroscopic parameters, which also account for 14N hyperfine splittings, we compile a line catalogue for each system up to 50 GHz as a preliminary and required step to characterize these molecules experimentally, whether in the laboratory or directly in the ISM. [ABSTRACT FROM AUTHOR]

Molecular ions are key intermediates in the build-up of chemical complexity in interstellar clouds. Among the more than 300 interstellar molecules, only eight negative ions, i.e. C2n+1N− (n  = 0–3) and HC2n− (n  = 2–5), have been astronomically observed. Understanding the formation mechanism of these ions under the interstellar conditions is essential for astrochemical modelling and establishing the astrochemical networks. Cyanopolyynes including the parent molecule HC3N are carbon-chain molecules that have been observed in a variety of astronomical objects such as the Titan's atmosphere. Herein, two cyanoacetylene anions HC3N‒ and CH3C3N‒ were generated in solid Ne matrix at 3 K and characterized with matrix-isolation infrared spectroscopy, as aided by isotopic substitutions and the ab initio calculations at the UCCSD(T)-F12a/cc-pVTZ-F12 level using second-order vibrational perturbation theory. Upon red-light irradiation at 625 nm, both ions undergo electron detachment by reformation of the neutral species. Importantly, the concomitant dehydrogenation of HC3N‒ has also been observed in the matrix, providing new insight into the intriguing mechanism for the formation of C3N‒ in the upper atmosphere of Titan. [ABSTRACT FROM AUTHOR]

Cross-sections and rate coefficients for rovibronic excitation of the CH+ ion by electron impact and dissociative recombination of CH+ with electrons are evaluated using a theoretical approach combining an R-matrix method and molecular quantum defect theory. The method has been developed and tested, comparing the theoretical results with the data from the recent Cryogenic Storage Ring experiment. The obtained cross-sections and rate coefficients evaluated for temperatures from 1 to 10 000 K could be used for plasma modelling in the interpretation of astrophysical observations and also in the technological applications where the molecular hydrocarbon plasma is present. [ABSTRACT FROM AUTHOR]

CCS(3Σ−) is one of the few molecules which presents many observable isotopologues, with the reported detection of 13CCS, C13CS, CC34S, and CC33S. The accurate determination of CCS isotopologues abundances enables the study of the isotopic fraction in media where they are detected, and gives insights into their formation pathways. The availability of collisional rate coefficients, that are prerequisite for accurate determination of their abundances in astrophysical media under non-local thermodynamic equilibrium (LTE) conditions, allows drawing reliable conclusions on their abundances. In this study, fine and hyperfine-structure resolved excitation rate coefficients induced by collisions with helium are produced with a quantum approach for all detected CCS isotopologues for the 5–50 K temperature range. Radiative transfer models have been performed with the new data to discuss their impact on the excitation conditions of these species. The effect of the isotopic substitution appears to be weak between fine-structure rate coefficients. The observed lines of CCS, 13CCS, C13CS, and CC34S are found to be out of LTE conditions, and therefore, the proper determination of the abundance of CCS isotopologues in molecular clouds requires the use of the data produced in this work. [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]

In this work, we focus on the study of radiation-induced desorption processes that occurred in acetonitrile ice irradiated by broad-band X-rays (6 eV to 2 keV) monitored by Fourier transform infrared spectroscopy at different radiation fluences. In a previous work, we used the procoda code to derive the chemical evolution of the ice. Here, we have observed that the acetonitrile desorbed column density is at least two orders of magnitude larger than the desorbed column densities of daughter or granddaughter molecular species at chemical equilibrium stage. This indicates that total desorption column density is mainly governed by the father molecule, as also previously hypothesized in experimental studies. This occurs basically because the acetonitrile column density is larger than the other ones. In particular, at chemical equilibrium acetonitrile desorption column density represents almost 98 per cent of the total, while it is close to 1  per cent for H, CN, and CH2, the species with larger molecular desorption percentages at chemical equilibrium. Another derived quantity is what we called intrinsic desorption rate, which is a number per second for individual species. Some of the larger intrinsic desorption rates were 6.2 × 10−6 (CH3CN), 6.2 × 10−6 (CN), 5.7 × 10−6 (H), 5.7 × 10−6 (CH2), and 4.4 × 10−6 (C2N2). These results help to put constraints in astrochemical models and can also be useful to clarify some astronomical radio observations. [ABSTRACT FROM AUTHOR]

This paper presents rate coefficients for transitions between rotational levels of the A-type and E-type nuclear spin modifications of methanol induced by collisions with molecular hydrogen. These rate coefficients are required for an accurate determination of methanol abundance in the interstellar medium, where local thermodynamic equilibrium conditions generally do not apply. Time-independent close-coupling quantum scattering calculations have been employed to calculate cross-sections and rate coefficients for the (de-)excitation of methanol in collisions with para - and ortho -H2. These calculations utilized a potential energy surface (PES) for the interaction of methanol with H2 recently computed by the explicitly correlated CCSD(T)-F12a coupled-cluster method that employed a correlation-consistent aug-cc-pVTZ basis. Rate coefficients for temperatures ranging from 3 to 250 K were calculated for all transitions among the first 76 rotational levels of both A-type and E-type methanol, whose energies are less than or equal to 170 K. These rate coefficients are compared with those by Rabli and Flower who carried out coupled-state calculations using a PES computed by second-order many-body perturbation theory. Simple radiative transfer calculations using the present set of rate coefficients are also reported and compared with such calculations using the rate coefficients previously computed by Rabli and Flower. [ABSTRACT FROM AUTHOR]

We report the derivation of rate coefficients for the rotational (de-)excitation of PO+ induced by collisions with H2. The calculations were performed on a 4D potential energy surface, obtained on top of highly accurate ab initio energy points. Preliminary tests pointed out the low influence of the coupling between j  = 0 and the higher rotational levels of H2 on the cross-sections values, thus allowing to neglect the rotational structure of H2. On this basis, state-to-state collisional rate coefficients were derived for temperatures ranging from 5 to 200 K. Radiative transfer calculations have been used to model the recent observation of PO+ in the G+0.693–0.027 molecular cloud, in order to evaluate the possible impact of non-LTE models on the determination of its physical conditions. The derived column density was found to be approximately ∼ 3.7 × 1011 cm−2, which is 60% (a factor of ∼ 1.7) smaller than the previously LTE-derived value. Extensive simulations show that PO+ low- j rotational lines exhibit maser behaviour at densities between 104 and 106 cm−3, thus highlighting the importance of a proper treatment of the molecular collisions to accurately model PO+ emissions in the interstellar medium. [ABSTRACT FROM AUTHOR]

We present cross-sections and rate coefficients for rotational transitions in the water isotopologues D2O, H |$_2^{18}$| O, and HDO induced by collisions with para-H2(j 2 = 0) and ortho-H2(j 2 = 1). Quantum scattering calculations are performed at the full close-coupling level with the isotopic variants of an accurate full-dimensional H2O−H2 interaction potential. The D2O, H |$_2^{18}$| O, and HDO cross-sections are compared to the corresponding cross-sections for H2O. Large isotopic effects are observed in the case of D2O and HDO, in particular for collisions with p-H2(j 2 = 0), while the 18O isotopic substitution is found to be negligible. Rate coefficients are provided for rotational transitions among all para-D2O, ortho-D2O, and HDO levels with internal energy below 300 cm−1 and for kinetic temperatures in the range 5–300 K. Non-LTE radiative transfer calculations show that the HDO 225.9 GHz and H |$_2^{18}$| O 203.4 GHz transitions recently detected with ALMA in the young proto-planetary disc V883 Ori should be inverted (weak masers) in a large fraction of the disc. [ABSTRACT FROM AUTHOR]

Quantum chemical cluster calculations employing density functional theory and correlation consistent basis sets reveal the following pathways by which hydroxide anions (OH–) may form in amorphous astrophysical ices: (1) hydroxyl radicals (OH), which may arise in ice via ultraviolet photolysis, can capture electrons; (2) adsorbed hydrogen atoms can capture electrons to form H–, which reacts with water to yield H2 and OH–; (3) NaOH deposited on ice dissociates into Na+ and OH–; (4) NaH deposited on ice dissociates into Na+ and H–; H– then reacts with water to yield H2 and OH– as above. The IR spectrum of ice-bound OH– is presented, based on nine clusters containing up to 31H2O and 1–2 OH– anions. The interaction of OH– in ice with cations is also explored. Prior work shows that when HCO+ is deposited on pure amorphous water clusters, it reacts with H2O to form formic acid (HCOOH) and the hydronium (H3O+). When HCO+ is deposited on a cluster containing OH–, the reaction proceeds in almost the same manner, but the H3O+ and OH– charge centres migrate through the water network toward each other and tend to neutralize one another by forming H2O. This occurred in all but one of seven cases considered; migration occurred even when the oxygen atom attacked by HCO+ is over 10 Å from the oxygen atom in OH–. Cations and anions can interact in ice via pathways not present in the gas phase or incorporated in current models. [ABSTRACT FROM AUTHOR]

'Hot atoms', atoms in their excited states, transfer their energy to the surrounding atmosphere through collisions. This process (known as thermalization) plays a crucial role in various astrophysical and atmospheric processes. Thermalization of hot atoms is mainly governed by the amount of species present in the surrounding atmosphere and the collision cross-sections between the hot atoms and surrounding species. In this work, we investigated the elastic and inelastic collisions between hot oxygen atoms and neutral N2 molecules, relevant to oxygen gas escape from the Martian atmosphere and for characterizing the chemical reactions in hypersonic flows. We conducted a series of quantum scattering calculations between various isotopes of O(3 P) atoms and N2 molecules across a range of collision energies (0.3–4 eV), and computed both their differential and collision cross-sections using quantum time-independent coupled-channel approach. Our differential cross-section results indicate a strong preference for forward scattering over sideways or backward scattering, and this anisotropy in scattering is further pronounced at higher collision energies. By comparing the cross-sections of three oxygen isotopes, we find that the heavier isotopes consistently have larger collision cross-sections than the lighter isotopes. As a whole, this study contributes to a better understanding of the energy distribution and thermalization processes of hot atoms within atmospheric environments. Specifically, the cross-sectional data presented in this work is directly useful in improving the accuracy of energy relaxation modelling of O and N2 collisions over the Mars and Venus atmospheres. [ABSTRACT FROM AUTHOR]

Ammonia is one of the most widely observed molecules in space, and many observations are able to resolve the hyperfine structure due to the electric quadrupole moment of the nitrogen nucleus. The observed spectra often display anomalies in the satellite components of the lines, which indicate substantial deviations from the local thermodynamic equilibrium. The interpretation of the spectra thus requires the knowledge of the rate coefficients for the hyperfine excitation of NH3 induced by collisions with H2 molecules, the dominant collider in the cold interstellar medium. In this paper, we present the first such calculations using a recoupling approach. The rate coefficients are obtained for all hyperfine levels within rotation–inversion levels up to j  = 4 and temperatures up to 100 K by means of quantum scattering close-coupling calculations on an accurate, five-dimensional, potential energy surface. We show that the rate coefficients depart significantly from those obtained with the statistical approach and that they do not conform to any simple propensity rules. Finally, we perform radiative transfer calculations to illustrate the impact of our new rate coefficients by modelling the hyperfine line intensities of the inversion transition in ground-state para -NH3 (jk  = 11) and of the rotational transition 10 → 00 in ortho -NH3. [ABSTRACT FROM AUTHOR]