Astrochemical Models Research Articles

Comprehensive laboratory constraints on thermal desorption of interstellar ice analogues

Gas accretion and sublimation in various astrophysical conditions are crucial aspects of our understanding of the chemical evolution of the interstellar medium. To explain grain growth and destruction in warm media, ice mantle formation and sublimation in cold media, and gas line emission spectroscopy, astrochemical models must mimic the gas--solid abundance ratio. Ice-sublimation mechanisms determine the position of snow lines and the nature of gas emitted by and locked inside planetary bodies in star-forming regions. To interpret observations from the interplanetary and extragalactic interstellar mediums, gas phase abundances must be modelled correctly. We provide a collection of thermal desorption data for interstellar ice analogues, aiming to put constraints on the trapping efficiency of water ice, as well as data that can be used to evaluate astrochemical models. We conduct experiments on compact, amorphous H$_2$O films, involving pure ices as well as binary and ternary mixtures. By manipulating parameters in a controlled way, we generate a set of benchmarks to evaluate both the kinetics and thermodynamics in astrochemical models. We conducted temperature-programmed desorption experiments with increasing order of complexity of ice analogues of various chemical compositions and surface coverages using molecular beams in ultrahigh vacuum conditions (1 times 10$^ $ hPa) and low temperatures (10 K). We provide TPD curves of pure ices made of Ar, CO, CO$_2$, NH$_3$, CH$_3$OH, H$_2$O, and NH$_4^+$HCOO$^-$, their binary ice mixtures with compact amorphous H$_2$O, ternary mixtures of H$_2$O : CH$_3$OH : CO, and a water ice made in situ to investigate its trapping mechanisms. Each experiment includes the experimental parameters, ice desorption kinetics for pure species, and the desorption yield (gas--solid ratio) for ice mixtures. From the desorption yields, we find common trends in the trapping of molecules when their abundance is compared to water: compact amorphous water ices are capable of trapping up to 20<!PCT!> of volatiles (Ar, CO, and CO$_2$), sim 3<!PCT!> of CH$_3$OH, and sim 5<!PCT!> NH$_3$ in relation to the water content within the ice matrix; ammonium formate is not trapped in the water ice films, and compact amorphous water ice formed in situ has similar trapping capabilities to a compact amorphous water ice deposited using molecular beams. Deposited or formed in a very compact structure, amorphous water ice of less than 100 layers cannot trap a large fraction of other gases, including CO and CO$_2$. These desorption yields offer insights into the availability of species that can react and form interstellar complex organic molecules during the warm-up phase of ice mantles. Furthermore, in order to be reliable, gas-grain astrochemical models should be able to reproduce the desorption kinetics and desorption yield presented in our benchmark laboratory experiments.

Interstellar Detection of O-protonated Carbonyl Sulfide, HOCS+

We present the first detection in space of O-protonated carbonyl sulfide (HOCS+), in the midst of an ultradeep molecular line survey toward the G+0.693-0.027 molecular cloud. From the observation of all K a = 0 transitions ranging from J lo = 2 to J lo = 13 of HOCS+ covered by our survey, we derive a column density of N = (9 ± 2) × 1012 cm−2, translating into a fractional abundance relative to H2 of ∼7 × 10−11. Conversely, the S-protonated HSCO+ isomer remains undetected, and we derive an upper limit to its abundance with respect to H2 of ≤3 × 10−11, a factor of ≥2.3 less abundant than HOCS+. We obtain an HOCS+/OCS ratio of ∼2.5 × 10−3, in good agreement with the prediction of astrochemical models. These models show that one of the main chemical routes to the interstellar formation of HOCS+ is likely the protonation of OCS, which appears to be more efficient at the oxygen end. Also, we find that high values of cosmic-ray ionization rates (10−15–10−14 s−1) are needed to reproduce the observed abundance of HOCS+. In addition, we compare the O/S ratio across different interstellar environments. G+0.693-0.027 appears as the source with the lowest O/S ratio. We find an HOCO+/HOCS+ ratio of ∼31, in accordance with other O/S molecular pairs detected toward this region and also close to the O/S solar value (∼37). This fact indicates that S is not significantly depleted within this cloud due to the action of large-scale shocks, unlike in other sources where S-bearing species remain trapped on icy dust grains.

Stability of solid-state formamide under Lyα irradiation

Context. Formamide (NH2CHO) plays a pivotal role as a crucial precursor to various prebiotic molecules, including sugars and nucleobases. To gain a deeper understanding of the chemical processes involving formamide formation in astrophysical settings, it becomes imperative to refine our comprehension through astrochemical models. These models necessitate not only the inclusion of pathways for formamide formation across diverse environments, but also the elucidation of mechanisms that lead to its degradation. Aims. The primary objective of this study is to scrutinize the influence of the underlying amorphous silicate substrate and the phase of formamide ice on the kinetics of its destruction and the resulting products upon exposure to Lyα (121.6 nm) radiation at 16 K. Methods. To achieve this, we conducted an examination of the photodestruction of NH2CHO ice, employing Fourier transform infrared spectroscopy. Results. Our findings reveal that, while the destruction rates of amorphous formamide ice remain consistent, regardless of the presence of an underlying amorphous olivine substrate, this substrate effectively reduces the formation of NH3, HNCO, and HCN within the ice following UV irradiation. On the other hand, contrary to common knowledge, crystalline formamide ice exhibits a considerably faster destruction rate, by an order of magnitude, than its amorphous counterpart under photo processing. Conclusions. In the interstellar medium, molecular ices often undergo phase changes depending on the environmental conditions. Our results indicate that crystalline formamide ice is more susceptible to rapid destruction than its amorphous counterpart, rendering it more elusive for detection within the lifetime of dense interstellar clouds. Furthermore, our findings emphasise the crucial significance of accounting for the influence of underlying dust grain surfaces in astrochemical models, as they have an effect on product formation during the degradation of molecular ices.

Relevance of the P+O2 Reaction for PO Formation in Astrochemical Environments: Electronic Structure Calculations and Kinetic Simulations

Phosphorus monoxide (PO) is a key brick of prebiotic chemistry since it is a potential precursor of phosphates, which are present in all living systems. Prompted by the lack of information on the different processes involved in the formation of PO, we have revisited and analyzed in detail the P(4 S) + O2(3Σ−) and P(4 S) + O2(1Δ) reactions leading to PO. The former process has been widely studied from both experimental and theoretical points of view, however, with contradictory results. We have used high-level quantum-chemical calculations to accurately describe the reaction mechanisms. Next, rate constants have been computed using a master equation approach based on ab initio transition state theory. By incorporating the P(4 S) + O2(3Σ−) reaction in an astrochemical model, we have found that this reaction cannot be overlooked when aiming at a complete understanding of the PO abundance in regions dominated by shocks with speeds below 40 km s−1.

Quantum Chemistry and Astrochemistry: A Match Made in the Heavens.

Quantum chemistry can uniquely answer astrochemical questions that no other technique can provide. Computations can be parallelized, automated, and left to run continuously providing exceptional molecular throughput that cannot be done through experimentation. Additionally, the granularity of the individual computations that are required of potential energy surfaces, reaction mechanism pathways, or other quantum chemically derived observables produces a unique mosaic that make up the larger whole. These pieces can be dissected for their individual contributions or evaluated in an ad hoc fashion for each of their roles in generating the larger whole. No other scientific approach is capable of reporting such fine-grained insights. Quantum chemistry also works from a bottom-up approach in providing properties directly from the desired molecule instead of a top-down perspective as required of experiment where molecules have to be linked to observed phenomena. Furthermore, modern quantum chemistry is well within the range of "chemical accuracy" and is approaching "spectroscopic accuracy." As such, the seemingly difficult questions asked by astrochemistry that would not be asked initially for any other application require quantum chemical reference data. While the results of quantum chemical computations are needed to interpret astrochemical observation, modeling, or laboratory experimentation, such hard questions, regardless of the original need to answer them, produce unique solutions. While questions in astrochemistry often require novel developments in and implementations of quantum chemistry as outlined herein, the applications of these solutions will stretch beyond astrochemistry and may yet impact fields much closer to Earth.

Can astronomical observations be used to constrain crucial chemical reactions? The methoxy case. SOLIS XVIII

ABSTRACT To understand the origin of interstellar molecules we rely on astrochemical models, the gas-phase networks of which contain ≥7000 reactions. However, just a tiny fraction of them have parameters derived in laboratory experiments. Theoretical quantum mechanical (QM) calculations can also provide this information. Unfortunately, sometimes theoretical predictions and experimental values disagree, as is the case for the paradigmatic reaction CH3OH + OH → CH3O + H2O. Both laboratory experiments and QM calculations found an unexpected increase in the rate coefficients with decreasing temperature. However, experimental and theoretical estimates of the rate coefficients diverge by up to two orders of magnitude at the low temperatures of interest in interstellar chemistry. This work aims to test whether astronomical observations can help untangle this confusing situation. To this end, we first carried out new QM calculations to derive the rate coefficients of the major destruction reaction of the methoxy radical, CH3O + H, and then we compared astronomical observations from the IRAM/NOEMA Large Programme SOLIS with astrochemical model predictions. Our new rate coefficient for the CH3O + H reaction is 5–10 times larger than that in the astrochemical data base KIDA in the 10–100 K range. When including the new methoxy destruction rate coefficients, the comparison between observations and model predictions favours the rate coefficients of the CH3OH + OH reaction from QM calculations. We conclude that QM calculations are an important alternative to laboratory experiments when it comes to the harsh conditions of interstellar objects and that astronomical observations can be used to constraint the rate coefficients of relevant reactions.

Study on Formation of Interstellar C7H from Reactions C4 + C3H2 and C4H + C3H.

We interrogated C7H produced from reactions C4 + C3H2/C4H + C3H → C7H + H using both translational and photoionization spectroscopy. Reactants C3H, C3H2, C4, and C4H were synthesized in two crossed beams of 1% C2H2/He ignited by pulsed high-voltage discharge. The individual contributions of reactions C4 + C3H2 and C4H + C3H to product C7H were evaluated as 17:83 from reactant concentrations in both molecular beams. The translational energy distribution, the angular distribution, and the photoionization efficiency curve of product C7H were unraveled. C7H was identified as the most stable linear isomer by its photoionization efficiency curve that features two ionization thresholds corresponding to separate transitions to singlet and triplet states of l-C7H+. The quantum-chemical calculations indicate that the associations of C4 with C3H2 and C4H with C3H incur no entrance barriers, and the most favorable exit channel leads to product l-C7H + H. It is the first time demonstrating that C7H is producible from reactions 1,3C4 + 1C3H2 and 2C4H + 2C3H on the lowest-lying singlet and triplet potential energy surfaces of 1,3C7H2. This work implies that the reactions of C4 + C3H2 and C4H + C3H might have contributions to interstellar C7H to some extent as compared with the C + C6H2 reaction commonly adopted in an astrochemical model.

Sensitivity analysis of aromatic chemistry to gas-phase kinetics in a dark molecular cloud model.

The increasingly large number of complex organic molecules detected in the interstellar medium necessitates robust kinetic models that can be relied upon for investigating the involved chemical processes. Such models require rate coefficients for each of the thousands of reactions; the values of these are often estimated or extrapolated, leading to large uncertainties that are rarely quantified. We have performed a global Monte Carlo and a more local one-at-a-time sensitivity analysis on the gas-phase rate coefficients in a 3-phase dark cloud model. Time-dependent sensitivities have been calculated using four metrics to determine key reactions for the overall network as well as for the cyanonaphthalene molecule in particular, an important interstellar species that is severely under-produced by current models. All four metrics find that reactions involving small, reactive species that initiate hydrocarbon growth have large effects on the overall network. Cyanonaphthalene is most sensitive to a number of these reactions as well as ring-formation of the phenyl cation (C6H5+) and aromatic growth from benzene to naphthalene. Future efforts should prioritize constraining rate coefficients of key reactions and expanding the network surrounding these processes. These results highlight the strength of sensitivity analysis techniques to identify critical processes in complex chemical networks, such as those often used in astrochemical modeling.

Stimulated radiative association of sodium and chlorine atoms and their ions in a coupled channel treatment.

In an extension of previous work (Šimsová et al., Phys. Chem. Chem. Phys., 2022, 24, 25250), we study stimulated radiative association of sodium chloride (NaCl) in an environment with a black body radiation. Colliding neutral (Na and Cl) and ionic (Na+ and Cl-) fragments are considered. The coupling between the diabatic ionic and neutral channels is accounted for. The cross sections are computed and resolved on the vibrational states of the formed NaCl molecule for detailed analysis. The thermal rate coefficients for neutral colliding fragments at kinetic temperatures, T, from 1 K to 5300 K are computed for use in astrochemical modelling. The total rate coefficient is affected by more than one order of magnitude by stimulated emission from a blackbody radiator of temperature Tb = 50 000 K. The effect from stimulated emission is largest for the lowest kinetic temperatures, where Tb of a few thousand kelvins has a significant effect. The rate coefficient for the colliding ionic fragments is calculated from 80 K to 3615 K. The blackbody radiation has little effect on this process.

Electronic energy transfer ionization in naphthalene-CO2 clusters reveals excited states of dry ice.

Electronic energy relaxation and transfer shapes the photochemistry in molecules and materials that are exposed to UV radiation in areas ranging from astrochemistry to biology. The interaction between CO2 and polycyclic aromatic hydrocarbons (PAHs) specifically, is of paramount interest in astrochemically relevant ices, the transition to renewable energy and the development of green chemistry. We investigate the vacuum UV excitation of the naphthalene-CO2 complex and observe excited states of CO2 through a newly identified molecular electronic energy transfer ionization mechanism. We evaluate the spectral development upon cluster growth with time-dependent density functional theory and show that the photoionization spectrum of naphthalene-CO2 closely resembles the photon-stimulated desorption spectrum of CO2 ice. The molecular electronic energy transfer ionization mechanism may affect the energy redistribution and charge balance in the interstellar medium significantly and therefore we discuss its implications for astrochemical models.

Shocking Sgr B2 (N1) with its own outflow

Aims. Because studies on complex organic molecules (COMs) in high-mass protostellar outflows are sparse, we want to investigate how a powerful outflow, such as that driven by the exciting source of the prominent hot core Sagittarius B2(N1), influences the gas molecular inventory of the surrounding medium with which it interacts. Identifying chemical differences to the hot core unaffected by the outflow and what causes them may help to better understand molecular segregation in other star-forming regions. Methods. We made use of the data taken as part of the 3 mm imaging spectral-line survey Re-exploring Molecular Complexity with ALMA (ReMoCA). We studied the morphology of the emission regions of simple and complex molecules in Sgr B2 (N1). For a selection of twelve COMs and four simpler species, spectra were modelled under the assumption of local thermodynamic equilibrium and population diagrams were derived at two positions, one in each lobe of the outflow. From this analysis, we obtained rotational temperatures and column densities. Abundances were subsequently compared to predictions of astrochemical models and to observations of L1157-B1, a position located in the well-studied outflow of the low-mass protostar L1157, and the source G+0.693-0.027 (G0.693), located in the Sgr B2 molecular cloud complex, which are other regions whose chemistry has been impacted by shocks. Results. Integrated intensity maps of SO and SiO emission reveal a bipolar structure with blue-shifted emission dominantly extending to the south-east from the centre of the hot core and red-shifted emission to the north-west. The morphology of both lobes is complex but can roughly be characterised by an emission component at a larger opening angle, containing most of the emission, and narrower features. The wider-angle component is also prominently observed in emission of S-bearing molecules and species that only contain N as a heavy element, including COMs, but also CH3OH, CH3CHO, HNCO, and NH2CHO. Rotational temperatures are found in the range of ~ 100–200 K. Abundances of N-bearing molecules with respect to CH3OH are enhanced in the outflow component compared to N1S, a position that is not impacted by the outflow. A comparison of molecular abundances with G+0.693–0.027 and L1157-B1 does not show any correlations, suggesting that a shock produced by the outflow impacts Sgr B2 (N1)’s material differently or that the initial conditions were different. Conclusions. The short distance of the analysed outflow positions to the centre of Sgr B2 (N1) lead us to propose a scenario in which a phase of hot-core chemistry (i.e. thermal desorption of ice species and high-temperature gas-phase chemistry) preceded a shock wave. The subsequent compression and further heating of the material resulted in the accelerated destruction of (mainly O-bearing) molecules. Gas-phase formation of cyanides seems to be able to compete with their destruction in the post-shock gas. The abundances of cyanopolyynes are enhanced in the outflow component pointing to (additional) gas-phase formation, possibly incorporating atomic N sourced from ammonia in the post-shock gas. To confirm such a scenario, chemical shock models need to be run that take into account the pre- and post-shock conditions of Sgr B2 (N1). In any case, the results provide new perspectives on shock chemistry and the importance of the environment in which it occurs.

Formation of Interstellar Complex Organic Molecules on Water-rich Ices Triggered by Atomic Carbon Freezing

The reactivity of interstellar carbon atoms (C) on water-dominated ices is one of the possible ways to form interstellar complex organic molecules (iCOMs). In this work, we report a quantum chemical study of the coupling reaction of C (3P) with an icy water molecule, alongside possible subsequent reactions with the most abundant closed-shell frozen species (NH3, CO, CO2, and H2), atoms (H, N, and O), and molecular radicals (OH, NH2, and CH3). We found that C reacts spontaneously with the water molecule, resulting in the formation of 3C–OH2, a highly reactive species due to its triplet electronic state. While reactions with the closed-shell species do not show any reactivity, reactions with N and O form CN and CO, respectively, the latter ending up in methanol upon subsequent hydrogenation. The reactions with OH, CH3, and NH2 form methanediol, ethanol, and methanimine, respectively, upon subsequent hydrogenation. We also propose an explanation for methane formation observed in experiments through additions of H to C in the presence of ices. The astrochemical implications of this work are: (i) atomic C on water ice is locked into 3C–OH2, making difficult the reactivity of bare C atoms on icy surfaces, contrary to what is assumed in current astrochemical models; and (ii) the extraordinary reactivity of 3C–OH2 provides new routes toward the formation of iCOMs in a nonenergetic way, in particular ethanol, the mother of other iCOMs once it is in the gas phase.

Low-Energy Electron Scattering from Pyrrole and Its Isomers.

Low-energy electron scattering from pyrrole and its isomers, such as 2-H pyrrole, cyclopropanecarbonitrile, and Z-2 butenenitrile, is explored in detail in this article. The electron interaction with the target molecules was studied through R-matrix theory. We have used minimal STO-3G and advanced DZP basis sets on a fine energy grid from 0.1 to 12 eV electron energy in the calculation. The properties of the STO-3G and DZP-based targets, such as their ionization energy, polarizability, dipole moment, rotational constant, principal moment of inertia, ground-state energy, and orbital energies, were investigated and compared to previously reported data. The elastic and inelastic channels showed the appearance of shape and Feshbach resonances for pyrrole and its isomers. The ultralow-energy region resonance was observed for Z-2 butenenitrile at 0.47 eV. With STO-3G and DZP basis sets, we estimated elastic, excitation, and momentum-transfer cross sections. The differential cross section for the present polar molecules was studied at 5 eV. The dissociative electron attachment channel for pyrrole and its isomers was studied for the pyrrolide anion. The data presented here will be helpful in astrophysical, astrochemical, atmospheric, and low-energy plasma modeling due to the presence of pyrrole and its isomers and the pyrrolide anion in the celestial bodies. The estimated data are also helpful in the biomedical field, radiation therapy, and pharmaceuticals.

SUNRISE: The rich molecular inventory of high-redshift dusty galaxies revealed by broadband spectral line surveys

Understanding the nature of high-redshift dusty galaxies requires a comprehensive view of their interstellar medium (ISM) and molecular complexity. However, the molecular ISM at high redshifts is commonly studied using only a few species beyond 12C16O, limiting our understanding. In this paper, we present the results of deep 3 mm spectral line surveys using the NOrthern Extended Millimeter Array (NOEMA) targeting two strongly lensed dusty galaxies observed when the Universe was less than 1.8 Gyr old: APM 08279+5255, a quasar at redshift z = 3.911, and NCv1.143 (H-ATLAS J125632.7+233625), a z = 3.565 starburst galaxy. The spectral line surveys cover rest-frame frequencies from about 330 to 550 GHz for both galaxies. We report the detection of 38 and 25 emission lines in APM 08279+5255 and NCv1.143, respectively. These lines originate from 17 species, namely CO, 13CO, C18O, CN, CCH, HCN, HCO+, HNC, CS, C34S, H2O, H3O+, NO, N2H+, CH, c-C3H2, and the vibrationally excited HCN and neutral carbon. The spectra reveal the chemical richness and the complexity of the physical properties of the ISM. By comparing the spectra of the two sources and combining the analysis of the molecular gas excitation, we find that the physical properties and the chemical imprints of the ISM are different: the molecular gas is more excited in APM 08279+5255, which exhibits higher molecular gas temperatures and densities compared to NCv1.143; the molecular abundances in APM 08279+5255 are akin to the values of local active galactic nuclei (AGN), showing boosted relative abundances of the dense gas tracers that might be related to high-temperature chemistry and/or the X-ray-dominated regions, while NCv1.143 more closely resembles local starburst galaxies. The most significant differences between the two sources are found in H2O: the 448 GHz ortho-H2O(423 − 330) line is significantly brighter in APM 08279+5255, which is likely linked to the intense far-infrared radiation from the dust powered by AGN. Our astrochemical model suggests that, at such high column densities, far-ultraviolet radiation is less important in regulating the ISM, while cosmic rays (and/or X-rays and shocks) are the key players in shaping the molecular abundances and the initial conditions of star formation. Both our observed CO isotopologs line ratios and the derived extreme ISM conditions (high gas temperatures, densities, and cosmic-ray ionization rates) suggest the presence of a top-heavy stellar initial mass function. From the ∼330–550 GHz continuum, we also find evidence of nonthermal millimeter flux excess in APM 08279+5255 that might be related to the central supermassive black hole. Such deep spectral line surveys open a new window into the physics and chemistry of the ISM and the radiation field of galaxies in the early Universe.

Spectroscopic characterization and photochemistry of HC3N− and CH3C3N−: implications for ion chemistry in Titan's atmosphere

ABSTRACT 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.

α-enhanced astrochemistry: the carbon cycle in extreme galactic conditions

ABSTRACT Astrochemistry has been widely developed as a power tool to probe the physical properties of the interstellar medium (ISM) in various conditions of the Milky Way (MW) Galaxy, and in near and distant galaxies. Most current studies conventionally apply linear scaling to all elemental abundances based on the gas-phase metallicity. However, these elements, including carbon and oxygen, are enriched differentially by stellar nucleosynthesis and the overall galactic chemical evolution, evident from α-enhancement in multiple galactic observations such as starbursts, high-redshift star-forming galaxies, and low-metallicity dwarfs. We perform astrochemical modelling to simulate the impact of an α-enhanced ISM gas cloud on the abundances of the three phases of carbon (C+, C, CO) dubbed as ‘the carbon cycle’. The ISM environmental parameters considered include two cosmic-ray ionization rates (ζCR = 10−17 and $10^{-15}\, {\rm s}^{-1}$), two isotropic FUV radiation field strengths (χ/χ0 = 1 and 102), and (sub-)linear dust-to-gas relations against metallicity, mimicking the ISM conditions of different galaxy types. In galaxies with [C/O] < 0, CO, C, and C+, all decrease in both abundances and emission, though with differential biases. The low-J CO emission is found to be the most stable tracer for the molecular gas, while C and C+ trace H2 gas only under limited conditions, in line with recent discoveries of [C i]-dark galaxies. We call for caution when using [C ii] $158\, \mu$m and [C i](1–0) as alternative H2-gas tracers for both diffuse and dense gas with non-zero [C/O] ratios.

Astrochemical Modeling of Propargyl Radical Chemistry in TMC-1

Recent detections of aromatic species in dark molecular clouds suggest that formation pathways may be efficient at very low temperatures and pressures, yet current astrochemical models are unable to account for their derived abundances, which can often deviate from model predictions by several orders of magnitude. The propargyl radical, a highly abundant species in the dark molecular cloud TMC-1, is an important aromatic precursor in combustion flames and possibly interstellar environments. We performed astrochemical modeling of TMC-1 using the three-phase gas-grain code NAUTILUS and an updated chemical network, focused on refining the chemistry of the propargyl radical and related species. The abundance of the propargyl radical has been increased by half an order of magnitude compared to the previous GOTHAM network. This brings it closer in line with observations, but it remains underestimated by 2 orders of magnitude compared to its observed value. Predicted abundances for the chemically related C4H3N isomers within an order of magnitude of observed values corroborate the high efficiency of CN addition to closed-shell hydrocarbons under dark molecular cloud conditions. The results of our modeling provide insight into the chemical processes of the propargyl radical in dark molecular clouds and highlight the importance of resonance-stabilized radicals in polycyclic aromatic hydrocarbon formation.

Characterization of acetonitrile ice irradiated by X-rays employing the procoda code – II. Desorption processes

ABSTRACT 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.

Deep Search for Molecular Oxygen in TW Hya

The dominant form of oxygen in cold molecular clouds is gas-phase carbon monoxide (CO) and ice-phase water (H2O). Yet, in planet-forming disks around young stars, gas-phase CO and H2O are less abundant relative to their interstellar medium values, and no other major oxygen-carrying molecules have been detected. Some astrochemical models predict that gas-phase molecular oxygen (O2) should be a major carrier of volatile oxygen in disks. We report a deep search for emission from the isotopologue 16O18O (N J = 21 − 01 line at 233.946 GHz) in the nearby protoplanetary disk around TW Hya. We used imaging techniques and matched filtering to search for weak emission but do not detect 16O18O. Based on our results, we calculate upper limits on the gas-phase O2 abundance in TW Hya of (6.4–70) × 10−7 relative to H, which is 2–3 orders of magnitude below solar oxygen abundance. We conclude that gas-phase O2 is not a major oxygen carrier in TW Hya. Two other potential oxygen-carrying molecules, SO and SO2, were covered in our observations, which we also do not detect. Additionally, we report a serendipitous detection of the C15N N J = 25/2 − 13/2 hyperfine transitions, F = 3 − 2 and F = 2 − 1, at 219.9 GHz, which we found via matched filtering and confirm through imaging.

Revised gas-phase formation network of methyl cyanide: the origin of methyl cyanide and methanol abundance correlation in hot corinos

ABSTRACT Methyl cyanide (CH3CN) is one of the most abundant and widely spread interstellar complex organic molecules (iCOMs). Several studies found that, in hot corinos, methyl cyanide and methanol abundances are correlated suggesting a chemical link, often interpreted as a synthesis of them on the interstellar grain surfaces. In this article, we present a revised network of the reactions forming methyl cyanide in the gas phase. We carried out an exhaustive review of the gas-phase CH3CN formation routes, propose two new reactions, and performed new quantum mechanics calculations of several reactions. We found that 13 of the 15 reactions reported in the databases KIDA and UDfA have incorrect products and/or rate constants. The new corrected reaction network contains 10 reactions leading to methyl cyanide. We tested the relative importance of those reactions in forming CH3CN using our astrochemical model. We confirm that the radiative association of CH3+ and HCN, forming CH3CNH+, followed by the electron recombination of CH3CNH+, is the most important CH3CN formation route in both cold and warm environments, notwithstanding that we significantly corrected the rate constants and products of both reactions. The two newly proposed reactions play an important role in warm environments. Finally, we found a very good agreement between the CH3CN predicted abundances with those measured in cold (∼10 K) and warm (∼90 K) objects. Unexpectedly, we also found a chemical link between methanol and methyl cyanide via the CH$_{3}^{+}$ ion, which can explain the observed correlation between the CH3OH and CH3CN abundances measured in hot corinos.