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  1. ABSTRACT

    Sodium-bearing species such as NaCl in the gas phase have been observed in an assortment of carbon-rich and oxygen-rich stellar atmospheres and interstellar environments such as the high-mass protostellar disc surrounding Orion Src1 and the proto-binary system, IRAS 16547−4247. Their detection in relatively low-temperature regions is yet to be made. In this paper, we consider the synthesis of sodium-bearing species with an emphasis on NaCl, via both gas-phase and grain-surface chemistry under assorted interstellar conditions. We also consider the chemistry leading to the gas-phase species NaH and NaOH. Two classes of numerical simulations were run: models under isothermal conditions at temperatures from 10 to 800 K with varied intervals, and three-phase warm-up models that consist of an initial isothermal collapse at 10 K, followed by a warm-up phase in which temperature rises linearly to 200 K, and finally a hot core phase. We have included reactive desorption for both models to produce gaseous NaCl, NaH, and NaOH. We found that for isothermal models over a broad parameter space, the fractional abundances of gaseous NaCl and NaOH can reach above 2 × 10−10 and approx. 1 × 10−10, respectively, are in the detection range of observational facilities such as Atacama Large Millimeter/Submillimeter Array and JWST. For warm-up models, we found that if we consider molecules to be co-desorbed with water, gaseous NaCl can have a sufficiently large abundance for detection. We then conclude that both gaseous NaCl and NaOH can be detected; however, more experiments and quantum mechanical calculations are needed to constrain the relevant reaction rates better.

     
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  2. Abstract

    The interplay of the chemistry and physics that exists within astrochemically relevant sources can only be fully appreciated if we can gain a holistic understanding of their chemical inventories. Previous work by Lee et al. demonstrated the capabilities of simple regression models to reproduce the abundances of the chemical inventory of the Taurus Molecular Cloud 1 (TMC-1), as well as to provide abundance predictions for new candidate molecules. It remains to be seen, however, to what degree TMC-1 is a “unicorn” in astrochemistry, where the simplicity of its chemistry and physics readily facilitates characterization with simple machine learning models. Here we present an extension in chemical complexity to a heavily studied high-mass star-forming region: the Orion Kleinmann–Low (Orion KL) nebula. Unlike TMC-1, Orion KL is composed of several structurally distinct environments that differ chemically and kinematically, wherein the column densities of molecules between these components can have nonlinear correlations that cause the unexpected appearance or even lack of likely species in various environments. This proof-of-concept study used similar regression models sampled by Lee et al. to accurately reproduce the column densities from the XCLASS fitting program presented by Crockett et al.

     
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  3. ABSTRACT

    Two closely related isomeric pairs of cyanides, CH3[CN/NC] and H2C[CN/NC], are studied in cold, dark interstellar cloud conditions. In contrast to the diverse detections of methyl cyanide (CH3CN) in space, methyl isocyanide (CH3NC) has previously only been observed in warm and hot star-forming regions. We report the detection of CH3NC in the cold pre-stellar core Taurus Molecular Cloud (TMC-1) using the Green Bank Telescope with a detection significance of 13.4σ. Hyperfine transitions in H2CCN and quadrupole interactions in CH3CN and CH3NC were matched to a spectral line survey from the Green Bank Telescope Observations of TMC-1: Hunting for Aromatic Molecules large project on the Green Bank Telescope, resulting in abundances with respect to hydrogen of $1.92^{+0.13}_{-0.07} \times 10^{-9}$ for the cyanomethyl radical (H2CCN), $5.02^{+3.08}_{-2.06} \times 10^{-10}$ for CH3CN, and $2.97^{+2.10}_{-1.37} \times 10^{-11}$ for CH3NC. Efforts to model these molecules with the three-phase gas-grain code nautilus in TMC-1 conditions overproduce both CH3CN and CH3NC, though the ratio of ∼5.9 per cent is consistent across observations and models of these species. This may point to missing destruction routes in the model. The models capture the larger abundance of H2CCN well. Dissociative recombination is found to be the primary production route for these molecules, and reactions with abundant ions are found to be the primary destruction routes. H + CH3NC is investigated with transition state theory as a potential destruction route, but found to be too slow in cold cloud conditions to account for the discrepancy in modelled and observed abundances of CH3NC.

     
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  4. Abstract We present Atacama Large Millimeter/submillimeter Array Band 3 data toward five massive young stellar objects (MYSOs), and investigate relationships between unsaturated carbon-chain species and saturated complex organic molecules (COMs). An HC 5 N ( J = 35–34) line has been detected from three MYSOs, where nitrogen (N)-bearing COMs (CH 2 CHCN and CH 3 CH 2 CN) have been detected. The HC 5 N spatial distributions show compact features and match with a methanol (CH 3 OH) line with an upper-state energy around 300 K, which should trace hot cores. The hot regions are more extended around the MYSOs where N-bearing COMs and HC 5 N have been detected compared to two MYSOs without these molecular lines, while there are no clear differences in the bolometric luminosity and temperature. We run chemical simulations of hot-core models with a warm-up stage, and compare with the observational results. The observed abundances of HC 5 N and COMs show good agreements with the model at the hot-core stage with temperatures above 160 K. These results indicate that carbon-chain chemistry around the MYSOs cannot be reproduced by warm carbon-chain chemistry, and a new type of carbon-chain chemistry occurs in hot regions around MYSOs. 
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    Free, publicly-accessible full text available June 27, 2024
  5. ABSTRACT

    The formation of complex organic molecules (COMs) in interstellar conditions is influenced by several different processes occurring both in the gas and solid phases. Here we perform an extension of previous work to understand the influence of electronically excited metastable species on condensed phase COM formation via insertion-type reactions. These reactions involve the insertion of a chemical entity on a previously existing chemical bond. Such insertion processes involving a metastable species allow for rapid reactions with the surrounding grain ice in the absence of activation energy or diffusion barriers even under cold, dark cloud conditions. In this paper, the production of a number of interstellar species including COMs in cold dark clouds is treated both via the metastable process as well as existing suggested pathways such as radical recombination and hydrogenation of unsaturated species in order to gain insight about the relative importance of the newly added process.

     
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  6. Abstract

    We report a comprehensive study of the cyanopolyyne chemistry in the prototypical prestellar core L1544. Using the 100 m Robert C. Byrd Green Bank Telescope, we observe three emission lines of HC3N, nine lines of HC5N, five lines of HC7N, and nine lines of HC9N. HC9N is detected for the first time toward the source. The high spectral resolution (∼0.05 km s−1) reveals double-peak spectral line profiles with the redshifted peak a factor 3–5 brighter. Resolved maps of the core in other molecular tracers indicate that the southern region is redshifted. Therefore, the bulk of the cyanopolyyne emission is likely associated with the southern region of the core, where free carbon atoms are available to form long chains, thanks to the more efficient illumination of the interstellar field radiation. We perform a simultaneous modeling of the HC5N, HC7N, and HC9N lines to investigate the origin of the emission. To enable this analysis, we performed new calculation of the collisional coefficients. The simultaneous fitting indicates a gas kinetic temperature of 5–12 K, a source size of 80″, and a gas density larger than 100 cm−3. The HC5N:HC7N:HC9N abundance ratios measured in L1544 are about 1:6:4. We compare our observations with those toward the well-studied starless core TMC-1 and with the available measurements in different star-forming regions. The comparison suggests that a complex carbon chain chemistry is active in other sources and is related to the presence of free gaseous carbon. Finally, we discuss the possible formation and destruction routes in light of the new observations.

     
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  7. ABSTRACT

    In the interstellar medium (ISM), the formation of complex organic molecules (COMs) is largely facilitated by surface reactions. However, in cold dark clouds, thermal desorption of COMs is inefficient because of the lack of thermal energy to overcome binding energies to the grain surface. Non-thermal desorption methods are therefore important explanations for the gas-phase detection of many COMs that are primarily formed on grains. Here, we present a new non-thermal desorption process: cosmic ray sputtering of grain ice surfaces based on water, carbon dioxide, and a simple mixed ice. Our model applies estimated rates of sputtering to the three-phase rate equation model nautilus-1.1, where this inclusion results in enhanced gas-phase abundances for molecules produced by grain reactions such as methanol (CH3OH) and methyl formate (HCOOCH3). Notably, species with efficient gas-phase destruction pathways exhibit less of an increase in models with sputtering compared to other molecules. These model results suggest that sputtering is an efficient, non-specific method of non-thermal desorption that should be considered as an important factor in future chemical models.

     
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  8. Abstract We report the detection of the lowest-energy conformer of E -1-cyano-1,3-butadiene ( E -1- C 4 H 5 CN ), a linear isomer of pyridine, using the fourth data reduction of the GBT Observations of TMC-1: Hunting for Aromatic Molecules (GOTHAM) deep spectral survey toward TMC-1 with the 100 m Green Bank Telescope. We perform velocity stacking and matched-filter analyses using Markov chain Monte Carlo simulations and find evidence for the presence of this molecule at the 5.1 σ level. We derive a total column density of 3.8 − 0.9 + 1.0 × 10 10 cm −2 , which is predominantly found toward two of the four velocity components we observe toward TMC-1. We use this molecule as a proxy for constraining the gas-phase abundance of the apolar hydrocarbon 1,3-butadiene. Based on the three-phase astrochemical modeling code NAUTILUS and an expanded chemical network, our model underestimates the abundance of cyano-1,3-butadiene by a factor of 19, with a peak column density of 2.34 × 10 10 cm −2 for 1,3-butadiene. Compared to the modeling results obtained in previous GOTHAM analyses, the abundance of 1,3-butadiene is increased by about two orders of magnitude. Despite this increase, the modeled abundances of aromatic species do not appear to change and remain underestimated by one to four orders of magnitude. Meanwhile, the abundances of the five-membered ring molecules increase proportionally with 1,3-butadiene by two orders of magnitude. We discuss the implications for bottom-up formation routes to aromatic and polycyclic aromatic molecules. 
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    Free, publicly-accessible full text available May 1, 2024
  9. The observation and synthesis of organic molecules in interstellar space is one of the most exciting and rapidly growing topics in astrochemistry. Spectroscopic observations especially with millimeter and submillimeter waves have resulted in the detection of more than 250 molecules in the interstellar clouds from which stars and planets are ultimately formed. In this review, we focus on the diverse suggestions made to explain the formation of Complex Organic Molecules (COMs) in the low-temperature interstellar medium. The dominant mechanisms at such low temperatures are still a matter of dispute, with both gas-phase and granular processes, occurring on and in ice mantles, thought to play a role. Granular mechanisms include both diffusive and nondiffusive processes. A granular explanation is strengthened by experiments at 10 K that indicate that the synthesis of large molecules on granular ice mantles under space-like conditions is exceedingly efficient, with and without external radiation. In addition, the bombardment of carbon-containing ice mantles in the laboratory by cosmic rays, which are mainly high-energy protons, can lead to organic species even at low temperatures. For processes on dust grains to be competitive at low temperatures, however, non-thermal desorption mechanisms must be invoked to explain why the organic molecules are detected in the gas phase. Although much remains to be learned, a better understanding of low-temperature organic syntheses in space will add both to our understanding of unusual chemical processes and the role of molecules in stellar evolution. 
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