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Binaries are known to play a key role in the mass loss and dynamical environments of evolved stars. Stellar and sub-stellar companion interactions produce complex wind morphologies including rotating/expanding disks, bipolar outflows, and spiral wind patterns; however, the connection between these many structures and the gas phase chemistry they harbor is not well-constrained. To expand the sample of chemical inventories in interacting systems, we present a detailed spectroscopic case study of the binary C-rich Asymptotic Giant Branch (AGB) star V Hya. Using spatially resolved ALMA observations at Bands 3, 6 and 7, we characterize the rotational emission lines and distributions of molecules in its surrounding disk undergoing dynamical expansion (DUDE). We detect emission from over 15 molecules and isotopologues toward this source, and present resolved maps for the brightest tracers of carbonaceous chemistry (e.g. CCH, C4H, HC5N, HNC, CH3CN). Employing LTE and non-LTE models of emission from the DUDE, we estimate the abundance distributions for optically thin species, and compare them with prototypical carbon-rich AGB envelopes. We find that the average abundances of detected species are within a factor of ${\sim}5$ from sources with similar mass-loss rates; however, the distribution of daughter species in V Hya is much more compact, with carbon chain species (CCH, C4H, HC3N) appearing with abundances $>$10$^{-7}$ even in the innermost sampled regions (200 au) of the disk., Comment: 40 pages, 27 figures, 2 appendices. Accepted for publication in ApJ

Polycyclic aromatic hydrocarbons (PAHs) are among the most ubiquitous compounds in the universe, accounting for up to ~25% of all interstellar carbon. Since most unsubstituted PAHs do not possess permanent dipole moments, they are invisible to radio astronomy. Constraining their abundances relies on the detection of polar chemical proxies, such as aromatic nitriles. We report the detection of 2- and 4-cyanopyrene, isomers of the recently detected 1-cyanopyrene. We find that these isomers are present in an abundance ratio of ~2:1:2, which mirrors the number of equivalent sites available for CN addition. We conclude that there is evidence that the cyanopyrene isomers formed by direct CN addition to pyrene under kinetic control in hydrogen-rich gas at 10 K and discuss constraints on the H/CN ratio for PAHs in TMC-1., Comment: Submitted version to comply with licensing agreements

Polycyclic aromatic hydrocarbons (PAHs) are expected to be the most abundant class of organic molecules in space. Their interstellar lifecycle is not well understood, and progress is hampered by difficulties detecting individual PAH molecules. Here, we present the discovery of CN-functionalized pyrene, a 4-ring PAH, in the dense cloud TMC-1 using the 100-m Green Bank Telescope. We derive an abundance of 1-cyanopyrene of ~1.52 x $10^{12}$ cm$^{-2}$, and from this estimate that the un-substituted pyrene accounts for up to ~0.03-0.3% of the carbon budget in the dense interstellar medium which trace the birth sites of stars and planets. The presence of pyrene in this cold (~10 K) molecular cloud agrees with its recent measurement in asteroid Ryugu where isotopic clumping suggest a cold, interstellar origin. The direct link to the birth site of our solar system is strengthened when we consider the solid state pyrene content in the pre-stellar materials compared to comets, which represent the most pristine material in the solar system. We estimate that solid state pyrene can account for 1% of the carbon within comets carried by this one single organic molecule. The abundance indicates pyrene is an "island of stability" in interstellar PAH chemistry and suggests a potential cold molecular cloud origin of the carbon carried by PAHs that is supplied to forming planetary systems, including habitable worlds such as our own., Comment: Version of manuscript revised to comply with licensing requirements

We used new high spectral resolution observations of propynal (HCCCHO) towards TMC-1 and in the laboratory to update the spectral line catalog available for transitions of HCCCHO - specifically at frequencies lower than 30 GHz which were previously discrepant in a publicly available catalog. The observed astronomical frequencies provided high enough spectral resolution that, when combined with high-resolution (~2 kHz) measurements taken in the laboratory, a new, consistent fit to both the laboratory and astronomical data was achieved. Now with a nearly exact (<1 kHz) frequency match to the J=2-1 and 3-2 transitions in the astronomical data, using a Markov chain Monte Carlo (MCMC) analysis, a best fit to the total HCCCHO column density of 7.28+4.08/-1.94 x 10^12 cm^-2 was found with a surprisingly low excitation temperature of just over 3 K. This column density is around a factor of 5 times larger than reported in previous studies. Finally, this work highlights that care is needed when using publicly available spectral catalogs to characterize astronomical spectra. The availability of these catalogs is essential to the success of modern astronomical facilities and will only become more important as the next generation of facilities come online., Comment: 14 pages, 5 figures, 5 Tables, 1 Appendix

Infrared emission features toward interstellar gas of the IC 348 star cluster in Perseus have been recently proposed to originate from the amino acid tryptophan. The assignment was based on laboratory infrared spectra of tryptophan pressed into pellets, a method which is known to cause large frequency shifts compared to the gas phase. We assess the validity of the assignment based on the original Spitzer data as well as new data from JWST. In addition, we report new spectra of tryptophan condensed in para-hydrogen matrices to compare with the observed spectra. The JWST MIRI data do not show evidence for tryptophan, despite deeper integration toward IC 348. In addition, we show that several of the lines attributed to tryptophan are likely due to instrumental artifacts. This, combined with the new laboratory data, allows us to conclude that there is no compelling evidence for the tryptophan assignment.

We use both chirped-pulse Fourier transform and frequency modulated absorption spectroscopy to study the rotational spectrum of 2-methoxyethanol in several frequency regions ranging from 8.7-500 GHz. The resulting rotational parameters permitted a search for this molecule in Atacama Large Millimeter/submillimeter Array (ALMA) observations toward the massive protocluster NGC 6334I as well as source B of the low-mass protostellar system IRAS 16293-2422. 25 rotational transitions are observed in the ALMA Band 4 data toward NGC 6334I, resulting in the first interstellar detection of 2-methoxyethanol. A column density of $1.3_{-0.9}^{+1.4} \times 10^{17}$ cm$^{-2}$ is derived at an excitation temperature of $143_{-39}^{+31}$ K. However, molecular signal is not observed in the Band 7 data toward IRAS 16293-2422B and an upper limit column density of $2.5 \times 10^{15}$ cm$^{-2}$ is determined. Various possible formation pathways--including radical recombination and insertion reactions--are discussed. We also investigate physical differences between the two interstellar sources that could result in the observed abundance variations., Comment: Accepted for publication in The Astrophysical Journal Letters

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. (2021) 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 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 non-linear 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. (2021) to accurately reproduce the column densities from the XCLASS fitting program presented in Crockett et al. (2014)., Comment: 14 pages; 6 figures, 1 table in the main text. 0 figures, 1 table in the appendix. Accepted for publication in The Astrophysical Journal. Molecular dataset for machine learning can be found in the Zenodo repository here: https://zenodo.org/record/7675609

A lower-than-solar elemental nitrogen content has been demonstrated for several comets, including 1P/Halley and 67P/C-G with independent in situ measurements of volatile and refractory budgets. The recently discovered semi-refractory ammonium salts in 67P/C-G are thought to be the missing nitrogen reservoir in comets. The thermal desorption of ammonium salts from cometary dust particles leads to their decomposition into ammonia and a corresponding acid. The NH$_{3}$/H$_{2}$O ratio is expected to increase with decreasing heliocentric distance with evidence for this in near-infrared observations. NH$_{3}$ has been claimed to be more extended than expected for a nuclear source. Here, the aim is to constrain the NH$_{3}$/H$_{2}$O ratio in comet C/2020 F3 (NEOWISE) during its July 2020 passage. OH emission from comet C/2020 F3 (NEOWISE) was monitored for 2 months with NRT and observed from GBT on 24 July and 11 August 2020. Contemporaneously with the 24 July 2020 OH observations, the NH$_{3}$ hyperfine lines were targeted with GBT. The concurrent GBT and NRT observations allowed the OH quenching radius to be determined at $\left(5.96\pm0.10\right)\times10^{4}$ km on 24 July 2020, which is important for accurately deriving $Q(\text{OH})$. C/2020 F3 (NEOWISE) was a highly active comet with $Q(\text{H}_{2}\text{O}) \approx 2\times10^{30}$ molec s$^{-1}$ one day before perihelion. The $3\sigma$ upper limit for $Q_{\text{NH}_{3}}/Q_{\text{H}_{2}\text{O}}$ is $<0.29\%$ at $0.7$ au from the Sun. The obtained NH$_{3}$/H$_{2}$O ratio is a factor of a few lower than measurements for other comets at such heliocentric distances. The abundance of NH$_{3}$ may vary strongly with time depending on the amount of water-poor dust in the coma. Lifted dust can be heated, fragmented, and super-heated; whereby, ammonium salts, if present, can rapidly thermally disintegrate and modify the NH$_{3}$/H$_{2}$O ratio., Comment: Accepted for publication in A&A; 18 pages, 8 figures, 6 tables

We report observations of the Didymos-Dimorphos binary asteroid system using the Atacama Large Millimeter/Submillimeter Array (ALMA) and the Atacama Compact Array (ACA) in support of the Double Asteroid Redirection Test (DART) mission. Our observations on UT 2022 September 15 provided a pre-impact baseline and the first measure of Didymos-Dimorphos' spectral emissivity at $\lambda=0.87$ mm, which was consistent with the handful of siliceous and carbonaceous asteroids measured at millimeter wavelengths. Our post-impact observations were conducted using four consecutive executions each of ALMA and the ACA spanning from T$+$3.52 to T$+$8.60 hours post-impact, sampling thermal emission from the asteroids and the impact ejecta. We scaled our pre-impact baseline measurement and subtracted it from the post-impact observations to isolate the flux density of mm-sized grains in the ejecta. Ejecta dust masses were calculated for a range of materials that may be representative of Dimorphos' S-type asteroid material. The average ejecta mass over our observations is consistent with 1.3--6.4$\times10^7$ kg, with the lower and higher values calculated for amorphous silicates and for crystalline silicates, respectively. Owing to the likely crystalline nature of S-type asteroid material, the higher value is favored. These ejecta masses represent 0.3--1.5\% of Dimorphos' total mass and are in agreement with lower limits on the ejecta mass based on measurements at optical wavelengths. Our results provide the most sensitive measure of mm-sized material in the ejecta and demonstrate the power of ALMA for providing supporting observations to spaceflight missions.

The extraordinary 2021 September-October outburst of Centaur 29P/Schwassmann-Wachmann 1 afforded an opportunity to test the composition of primitive Kuiper disk material at high sensitivity. We conducted nearly simultaneous multi-wavelength spectroscopic observations of 29P/Schwassmann-Wachmann 1 using iSHELL at the NASA Infrared Telescope Facility and nFLASH at the Atacama Pathfinder EXperiment (APEX) on 2021 October 6, with follow-up APEX/nFLASH observations on 2021 October 7 and 2022 April 3. This coordinated campaign between near-infrared and radio wavelengths enabled us to sample molecular emission from a wealth of coma molecules and to perform measurements that cannot be accomplished with either wavelength alone. We securely detected CO emission on all dates with both facilities, including velocity-resolved spectra of the CO (J=2-1) transition with APEX/nFLASH and multiple CO (v=1-0) rovibrational transitions with IRTF/iSHELL. We report rotational temperatures, coma kinematics, and production rates for CO and stringent (3-sigma) upper limits on abundance ratios relative to CO for CH4, C2H6, CH3OH, H2CO, CS, and OCS. Our upper limits for CS/CO and OCS/CO represent their first values in the literature for this Centaur. Upper limits for CH4, C2H6, CH3OH, and H2CO are the most stringent reported to date, and are most similar to values found in ultra CO-rich Oort cloud comet C/2016 R2 (PanSTARRS), which may have implications for how ices are preserved in cometary nuclei. We demonstrate the superb synergy of coordinated radio and near-infrared measurements, and advocate for future small body studies that jointly leverage the capabilities of each wavelength.

In recent years, many questions have arisen regarding the chemistry of photochemical products in the carbon-rich winds of evolved stars. To address them, it is imperative to constrain the distributions of such species through high angular resolution interferometric observations covering multiple rotational transitions. We used archival ALMA observations to map rotational lines involving high energy levels of cyanoacetylene (HC$_3$N) toward the inner envelope (radius <8"/1000 AU) of the carbon star IRC+10216. The observed lines include the J=28-27, J=30-29, and J=38-37, transitions of HC$_3$N in its ground vibrational state. In contrast to previous observations of linear carbon chains toward this AGB star which show extended, hollow emission at 15"-20" radii (e.g. C$_4$H, C$_6$H, HC$_5$N), the maps of the HC$_3$N lines here show compact morphologies comprising various arcs and density enhancements, with significant emission from gas clumps at an angular distance of ~3" (350 AU) from the central AGB star. We compared visibility sampled non-LTE radiative transfer models with the observed brightness distributions, and derive a fractional abundance with respect to H$_2$ of $10^{-8}$ for HC$_3$N at the radii probed by these lines. These results are consistent with enhanced photochemistry occurring in warm (~200 K) regions of the circumstellar envelope. After application of a specialized chemical model for IRC+10216, we find evidence that the enhanced HC$_3$N abundances in the inner wind are most likely due to a solar-type binary companion initiating photochemistry in this region., Comment: 17 pages, 9 figures, 2 tables. Accepted for publication in ApJ

We present laboratory rotational spectroscopy of five isomers of cyanoindene (2-, 4-, 5-, 6-, and 7-cyanoindene) using a cavity Fourier-transform microwave spectrometer operating between 6-40 GHz. Based on these measurements, we report the detection of 2-cyanoindene (1H-indene-2-carbonitrile; 2-C$_9$H$_7$CN) in GOTHAM line survey observations of the dark molecular cloud TMC-1 using the Green Bank Telescope at centimeter wavelengths. Using a combination of Markov Chain Monte Carlo (MCMC), spectral stacking, and matched filtering techniques, we find evidence for the presence of this molecule at the 6.3$\sigma$ level. This provides the first direct observation of the ratio of a cyano-substituted polycyclic aromatic hydrocarbon (PAH) to its pure hydrocarbon counterpart, in this case indene, in the same source. We discuss the possible formation chemistry of this species, including why we have only detected one of the isomers in TMC-1. We then examine the overall hydrocarbon:CN-substituted ratio across this and other simpler species, as well as compare to those ratios predicted by astrochemical models. We conclude that while astrochemical models are not yet sufficiently accurate to reproduce absolute abundances of these species, they do a good job at predicting the ratios of hydrocarbon:CN-substituted species, further solidifying -CN tagged species as excellent proxies for their fully-symmetric counterparts., Comment: Accepted in ApJL

We have conducted an extensive search for nitrogen-, oxygen- and sulfur-bearing heterocycles toward Taurus Molecular Cloud 1 (TMC-1) using the deep, broadband centimeter-wavelength spectral line survey of the region from the GOTHAM large project on the Green Bank Telescope. Despite their ubiquity in terrestrial chemistry, and the confirmed presence of a number of cyclic and polycyclic hydrocarbon species in the source, we find no evidence for the presence of any heterocyclic species. Here, we report the derived upper limits on the column densities of these molecules obtained by Markov Chain Monte Carlo (MCMC) analysis and compare this approach to traditional single-line upper limit measurements. We further hypothesize why these molecules are absent in our data, how they might form in interstellar space, and the nature of observations that would be needed to secure their detection., Comment: Accepted in the Journal of Physical Chemistry A

We report a systematic study of all known methyl carbon chains toward TMC-1 using the second data release of the GOTHAM survey, as well as a search for larger species. Using Markov-Chain Monte Carlo simulations and spectral line stacking of over 30 rotational transitions, we report statistically significant emission from methylcyanotriacetylene (CH$_3$C$_7$N) at a confidence level of 4.6$\sigma$, and use it to derive a column density of ${\sim}$10$^{11}$ cm$^{-2}$. We also searched for the related species, methyltetraacetylene (CH$_3$C$_8$H), and place upper limits on the column density of this molecule. By carrying out the above statistical analyses for all other previously detected methyl-terminated carbon chains that have emission lines in our survey, we assess the abundances, excitation conditions, and formation chemistry of methylpolyynes (CH3C$_{2n}$H) and methylcyanopolyynes (CH3C$_{2n-1}$N) in TMC-1, and compare those with predictions from a chemical model. Based on our observed trends in column density and relative populations of the A and E nuclear spin isomers, we find that the methylpolyynes and methylcyanopolyynes families exhibit stark differences from one another, pointing to separate interstellar formation pathways, which is confirmed through gas-grain chemical modeling with nautilus., Comment: 15 pages, 7 figures. Accepted for publication in ApJ

We report the first survey of molecular emission from cometary volatiles using standalone Atacama Compact Array (ACA) observations of the Atacama Large Millimeter/Submillimeter Array (ALMA) toward comet C/2015 ER61 (PanSTARRS) carried out on UT 2017 April 11 and 15, shortly after its April 4 outburst. These measurements of HCN, CS, CH$_3$OH, H$_2$CO, and HNC (along with continuum emission from dust) probed the inner coma of C/2015 ER61, revealing asymmetric outgassing and discerning parent from daughter/distributed source species. This work presents spectrally integrated flux maps, autocorrelation spectra, production rates, and parent scale lengths for each molecule, and a stringent upper limit for CO. HCN is consistent with direct nucleus release in C/2015 ER61, whereas CS, H$_2$CO, HNC, and potentially CH$_3$OH are associated with distributed sources in the coma. Adopting a Haser model, parent scale lengths determined for H$_2$CO (L$_p$ $\sim$ 2200 km) and HNC (L$_p$ $\sim$ 3300 km) are consistent with previous work in comets, whereas significant extended source production (L$_p$ $\sim$ 2000 km) is indicated for CS, suggesting production from an unknown parent in the coma. The continuum presents a point-source distribution, with a flux density implying an excessively large nucleus, inconsistent with other estimates of the nucleus size. It is best explained by the thermal emission of slowly-moving outburst ejectas, with total mass 5--8 $\times$ 10$^{10}$ kg. These results demonstrate the power of the ACA for revealing the abundances, spatial distributions, and locations of molecular production for volatiles in moderately bright comets such as C/2015 ER61.

Ubiquitous unidentified infrared emission bands are seen in many astronomical sources. Although these bands are widely, if not unanimously, attributed to the collective emission from polycyclic aromatic hydrocarbons, no single species from this class has been detected in space. We present the discovery of two -CN functionalized polycyclic aromatic hydrocarbons, 1- and 2-cyanonaphthalene, in the interstellar medium aided by spectral matched filtering. Using radio observations with the Green Bank Telescope, we observe both bi-cyclic ring molecules in the molecular cloud TMC-1. We discuss potential in situ gas-phase formation pathways from smaller organic precursor molecules.

We report the detection of CH$_3$OH emission in comet 46P/Wirtanen on UT 2018 December 8 and 9 using the Atacama Compact Array (ACA), part of the Atacama Large Millimeter/Submillimeter Array (ALMA). These interferometric measurements of CH$_3$OH along with continuum emission from dust probed the inner coma ($<$2000 km from the nucleus) of 46P/Wirtanen approximately one week before its closest approach to Earth ($\Delta$ = 0.089 -- 0.092 au), revealing rapidly varying and anisotropic CH$_3$OH outgassing during five separate ACA executions between UT 23:57 December 7 and UT 04:55 December 9, with a clear progression in the spectral line profiles over a timescale of minutes. We present spectrally integrated flux maps, production rates, rotational temperatures, and spectral line profiles of CH$_3$OH during each ACA execution. The variations in CH$_3$OH outgassing are consistent with Wirtanen's 9 hr nucleus rotational period derived from optical and millimeter wavelength measurements and thus are likely coupled to the changing illumination of active sites on the nucleus. The consistent blue offset of the line center indicates enhanced CH$_3$OH sublimation from the sunward hemisphere of the comet, perhaps from icy grains. These results demonstrate the exceptional capabilities of the ACA for time-resolved measurements of comets such as 46P/Wirtanen.

Much like six-membered rings, five-membered rings are ubiquitous in organic chemistry, frequently serving as the building blocks for larger molecules, including many of biochemical importance. From a combination of laboratory rotational spectroscopy and a sensitive spectral line survey in the radio band toward the starless cloud core TMC-1, we report the astronomical detection of 1-cyano-1,3-cyclopentadiene, $c$-C$_5$H$_5$CN}, a highly polar, cyano derivative of cyclopentadiene, $c$-C$_5$H$_6$. The derived abundance of $c$-C$_5$H$_5$CN} is far greater than predicted from astrochemical models which well reproduce the abundance of many carbon chains. This finding implies either an important production mechanism or a large reservoir of aromatic material may need to be considered. The apparent absence of its closely-related isomer, 2-cyano-1,3-cyclopentadiene, may arise from its lower stability or be indicative of a more selective pathway for formation of the 1-cyano isomer, perhaps one starting from acyclic precursors. The absence of N-heterocycles such as pyrrole and pyridine is discussed in light of the astronomical finding., Comment: Accepted for publication in Nature Astronomy. 36 pages comprising five figures, two tables, five supplementary tables, and six supplementary figures

Benzonitrile ($c$-C$_6$H$_5$CN), a polar proxy for benzene ($c$-C$_6$H$_6$}), has the potential to serve as a highly convenient radio probe for aromatic chemistry, provided this ring can be found in other astronomical sources beyond the molecule-rich prestellar cloud TMC-1 where it was first reported by McGuire et al. in 2018. Here we present radio astronomical evidence of benzonitrile in four additional pre-stellar, and possibly protostellar, sources: Serpens 1A, Serpens 1B, Serpens 2, and MC27/L1521F. These detections establish benzonitrile is not unique to TMC-1; rather aromatic chemistry appears to be widespread throughout the earliest stages of star formation, likely persisting at least to the initial formation of a protostar. The abundance of benzonitrile far exceeds predictions from models which well reproduce the abundances of carbon chains, such as HC$_7$N, a cyanpolyyne with the same heavy atoms, indicating the chemistry responsible for planar carbon structures (as opposed to linear ones) in primordial sources is favorable but not well understood. The abundance of benzonitrile relative to carbon-chain molecules displays sizable variations between sources within the Taurus and Serpens clouds, implying the importance of physical conditions and initial elemental reservoirs of the clouds themselves., Comment: To Appear in Nature Astronomy, 53 Pages, 15 Figures, 12 Tables

As the inventory of interstellar molecules continues to grow, the gulf between small species, whose individual rotational lines can be observed with radio telescopes, and large ones, such as polycyclic aromatic hydrocarbons (PAHs) best studied in bulk via infrared and optical observations, is slowly being bridged. Understanding the connection between these two molecular reservoirs is critical to understanding the interstellar carbon cycle, but will require pushing the boundaries of how far we can probe molecular complexity while still retaining observational specificity. Toward this end, we present a method for detecting and characterizing new molecular species in single-dish observations toward sources with sparse line spectra. We have applied this method to data from the ongoing GOTHAM (GBT Observations of TMC-1: Hunting Aromatic Molecules) Green Bank Telescope (GBT) large program, discovering six new interstellar species. In this paper we highlight the detection of HC$_{11}$N, the largest cyanopolyyne in the interstellar medium., Comment: 42 pages, 36 figures, 9 tables, to appear in Nature Astronomy

We present an overview of the GOTHAM (GBT Observations of TMC-1: Hunting Aromatic Molecules) Large Program on the Green Bank Telescope. This and a related program were launched to explore the depth and breadth of aromatic chemistry in the interstellar medium at the earliest stages of star formation, following our earlier detection of benzonitrile ($c$-C$_6$H$_5$CN) in TMC-1. In this work, details of the observations, use of archival data, and data reduction strategies are provided. Using these observations, the interstellar detection of propargyl cyanide (HCCCH$_2$CN) is described, as well as the accompanying laboratory spectroscopy. We discuss these results, and the survey project as a whole, in the context of investigating a previously unexplored reservoir of complex, gas-phase molecules in pre-stellar sources. A series of companion papers describe other new astronomical detections and analyses., Comment: Accepted in the Astrophysical Journal Letters

We report an astronomical detection of HC$_4$NC for the first time in the interstellar medium with the Green Bank Telescope toward the TMC-1 molecular cloud with a minimum significance of $10.5 \sigma$. The total column density and excitation temperature of HC$_4$NC are determined to be $3.29^{+8.60}_{-1.20}\times 10^{11}$ cm$^{-2}$ and $6.7^{+0.3}_{-0.3}$ K, respectively, using the MCMC analysis. In addition to HC$_4$NC, HCCNC is distinctly detected whereas no clear detection of HC$_6$NC is made. We propose that the dissociative recombination of the protonated cyanopolyyne, HC$_5$NH$^+$, and the protonated isocyanopolyyne, HC$_4$NCH$^+$, are the main formation mechanisms for HC$_4$NC while its destruction is dominated by reactions with simple ions and atomic carbon. With the proposed chemical networks, the observed abundances of HC$_4$NC and HCCNC are reproduced satisfactorily., Comment: Accepted in the Astrophysical Journal Letters

Amide molecules produced in space could play a key role in the formation of biomolecules on a young planetary object. However, the formation and chemical network of amide molecules in space is not well understood. In this work, ALMA observations are used to study a number of amide(-like) molecules toward the high-mass star-forming region NGC 6334I. The first detections of cyanamide (NH$_{2}$CN), acetamide (CH$_{3}$C(O)NH$_{2}$) and N-methylformamide (CH$_{3}$NHCHO) are presented for this source. These are combined with analyses of isocyanic acid (HNCO) and formamide (NH$_{2}$CHO) and a tentative detection of urea (carbamide; NH$_{2}$C(O)NH$_{2}$). Abundance correlations show that most amides are likely formed in related reactions occurring in ices on interstellar dust grains in NGC 6334I. However, in an expanded sample of sources, large abundance variations are seen for NH$_{2}$CN that seem to depend on the source type, which suggests that the physical conditions within the source heavily influence the production of this species. The rich amide inventory of NGC 6334I strengthens the case that interstellar molecules can contribute to the emergence of biomolecules on planets., Comment: Accepted for publication in The Astrophysical Journal

We report a search for the diatomic hydrides SiH, PH, and FeH along the line of sight toward the chemically rich circumstellar envelopes of IRC+10216 and VY Canis Majoris. These molecules are thought to form in high temperature regions near the photospheres of these stars, and may then further react via gas-phase and dust-grain interactions leading to more complex species, but have yet to be constrained by observation. We used the GREAT spectrometer on SOFIA to search for rotational emission lines of these molecules in four spectral windows ranging from 600 GHz to 1500 GHz. Though none of the targeted species were detected in our search, we report their upper limit abundances in each source and discuss how they influence the current understanding of hydride chemistry in dense circumstellar media. We attribute the non-detections of these hydrides to their compact source sizes, high barriers of formation, and proclivity to react with other molecules in the winds., Comment: Accepted for publication in ApJ. 14 pages, 4 figures, 3 tables

A long standing problem in astrochemistry is the inability of many current models to account for missing sulfur content. Many relatively simple species that may be good candidates to sequester sulfur have not been measured experimentally at the high spectral resolution necessary to enable radioastronomical identification. On the basis of new laboratory data, we report searches for the rotational lines in the microwave, millimeter, and sub-millimeter regions of the sulfur-containing hydrocarbon HCCSH. This simple species would appear to be a promising candidate for detection in space owing to the large dipole moment along its $b$-inertial axis, and because the bimolecular reaction between two highly abundant astronomical fragments (CCH and SH radicals) may be rapid. An inspection of multiple line surveys from the centimeter to the far-infrared toward a range of sources from dark clouds to high-mass star-forming regions, however, resulted in non-detections. An analogous search for the lowest-energy isomer, H$_2$CCS, is presented for comparison, and also resulted in non-detections. Typical upper limits on the abundance of both species relative to hydrogen are $10^{-9}$-$10^{-10}$. We thus conclude that neither isomer is a major reservoir of interstellar sulfur in the range of environments studied. Both species may still be viable candidates for detection in other environments or at higher frequencies, providing laboratory frequencies are available., Comment: Accepted in the Astrophysical Journal

Vibrationally excited states of detected interstellar molecules have been shown to account for a large portion of unidentified spectral lines in observed interstellar spectra toward chemically rich sources. Here, we present the first interstellar detection of the first and second vibrationally excited torsional states of acetic acid ($v_\mathrm{t} = 1, 2$) toward the high-mass star-forming region NGC 6334I. The observations presented were taken with the Atacama Large Millimeter/submillimeter Array in bands 4, 6, and 7 covering a frequency range of 130 - 352 GHz. By comparing a single excitation temperature model to the observations, the best-fit excitation temperature and column density are obtained to be 142(25) K and $1.12(7) \times 10^{17} \mathrm{cm^{-2}}$ respectively. Based on the intensity maps of the vibrationally excited CH$_3$COOH transitions, we found that the CH$_3$COOH emissions are compact and concentrated toward the MM1 and MM2 regions with a source size smaller than 2 arcsec. After locating the emission from different CH$_3$COOH transitions, which cover a large range of excitation energies, we are able to explain the variation of the CH$_3$COOH emission peak within the MM2 core by invoking continuum absorption or outflows., Comment: 15 pages, 5 figures

Shocks are a crucial probe for understanding the ongoing chemistry within ices on interstellar dust grains where many complex organic molecules (COMs) are believed to be formed. However, previous work has been limited to the initial liberation into the gas phase through non-thermal desorption processes such as sputtering. Here, we present results from the adapted three-phase gas-grain chemical network code NAUTILUS, with the inclusion of additional high-temperature reactions, non-thermal desorption, collisional dust heating, and shock-physics parameters. This enhanced model is capable of reproducing many of the molecular distributions and abundance ratios seen in our prior observations of the prototypical shocked-outflow L1157. In addition, we find that, among others, NH$_2$CHO, HCOOCH$_3$, and CH$_3$CHO have significant post-shock chemistry formation routes that differ from those of many other COMs observed in shocks. Finally, a number of selected species and phenomena are studied here with respect to their usefulness as shock tracers in various astrophysical sources., Comment: 20 pages, 10 figures, Accepted for publication in The Astrophysical Journal

The C$_2$H$_4$O$_2$ isomers have been previously investigated primarily via disparate sets of observations involving single dish and array measurements. The only attempt at using a uniform set of observations was performed with the IRAM 30 m observation in 2013 (Belloche et al. 2013). In this study, we present an intensive and rigorous spectral and morphological analysis of the C$_2$H$_4$O$_2$ isomers towards Sgr B2(N) with interferometers, ALMA Band 3 observations. We propose a quantitative selection method, which automates the determination of the most uncontaminated transitions and allows us to report the discovery of previously undetected transitions of the three isomers. With the least contaminated transitions, the high spatial-resolution millimeter maps of the C$_2$H$_4$O$_2$ isomers reveal that HCOOCH$_3$ and CH$_2$OHCHO each display two different velocity components, while only one velocity component of CH$_3$COOH is resolved. Moreover, the distribution of HCOOCH$_3$ is extended and offset from the continuum emission, unlike CH$_2$OHCHO and CH$_3$COOH, for which the low-velocity component is found to be compact and concentrated toward the continuum emission peak of Sgr B2(N). The distinct morphologies of these C$_2$H$_4$O$_2$ isomeric species indicate that HCOOCH$_3$ have significant differences in chemical processes than CH$_2$OHCHO and CH$_3$COOH, which display similar spatial distributions., Comment: 60 pages, 16 figures

One of the primary mechanisms for inferring the dynamical history of planets in our Solar System and in exoplanetary systems is through observation of elemental ratios (i.e. C/O). The ability to effectively use these observations relies critically on a robust understanding of the chemistry and evolutionary history of the observed abundances. Significant efforts have been devoted to this area from within astrochemistry circles, and these efforts should be supported going forward by the larger exoplanetary science community. In addition, the construction of a next-generation radio interferometer will be required to test many of these predictive models in situ, while simultaneously providing the resolution necessary to pinpoint the location of planets in formation., Comment: To be published in the ASP Monograph Series, "Science with a Next-Generation VLA", ed. E. J. Murphy (ASP, San Francisco, CA)

We present the first results of a pilot program to conduct an ALMA Band 10 spectral line survey of the high-mass star-forming region NGC 6334I. The observations were taken in exceptional weather conditions (0.19 mm precipitable water) with typical system temperatures $T_{\rm{sys}}$ $<$950 K at $\sim$890 GHz. A bright, bipolar north-south outflow is seen in HDO and CS emission, driven by the embedded massive protostar MM1B. This has allowed, for the first time, a direct comparison of the thermal water in this outflow to the location of water maser emission from prior 22 GHz VLA observations. The maser locations are shown to correspond to the sites along the outflow cavity walls where high velocity gas impacts the surrounding material. We also compare our new observations to prior Herschel HIFI spectral line survey data of this field, detecting an order of magnitude more spectral lines (695 vs 65) in the ALMA data. We focus on the strong detections of the complex organic molecule glycolaldehyde (HC(O)CH$_2$OH) in the ALMA data that is not detected in the heavily beam-diluted HIFI spectra. Finally, we stress the need for dedicated THz laboratory spectroscopy to support and exploit future high-frequency molecular line observations with ALMA., Comment: Accepted in ApJ Letters

The inelastic cross sections and rate coefficients for the rotational excitation of methanimine (CH$_2$NH) by cold H$_2$ have been determined quantum mechanically based on a new highly correlated five-dimensional potential energy surface. This surface was fitted to more than 60 000 ab initio points with a root mean square error of $\sim$ 1-2 cm$^{-1}$ in the region of the potential well whose depth is -374.0 cm$^{-1}$. The rotationally inelastic rate coefficients have been combined with spectroscopic data to generate the non-equilibrium spectrum of CH$_2$NH towards the interstellar molecular cloud Sgr~B2(N). The transition $1_{10}\to 1_{11}$ at 5.29 GHz is found to be inverted and the predicted weak maser emission spectrum is in excellent agreement with new observations performed with the 100-meter Green Bank Telescope., Comment: 16 pages, 4 figures

Polycyclic aromatic hydrocarbons and polycyclic aromatic nitrogen heterocycles are thought to be widespread throughout the Universe, because these classes of molecules are probably responsible for the unidentified infrared bands, a set of emission features seen in numerous Galactic and extragalactic sources. Despite their expected ubiquity, astronomical identification of specific aromatic molecules has proven elusive. We present the discovery of benzonitrile ($c$-C$_6$H$_5$CN), one of the simplest nitrogen-bearing aromatic molecules, in the interstellar medium. We observed hyperfine-resolved transitions of benzonitrile in emission from the molecular cloud TMC-1. Simple aromatic molecules such as benzonitrile may be precursors for polycyclic aromatic hydrocarbon formation, providing a chemical link to the carriers of the unidentified infrared bands.

We report the detection of interstellar methoxymethanol (CH$_3$OCH$_2$OH) in ALMA Bands 6 and 7 toward the MM1 core in the high-mass star-forming region NGC 6334I at ~0.1" - 1" spatial resolution. A column density of 4(2) x $10^{18}$ cm$^{-2}$ at $T_{ex}$ = 200 K is derived toward MM1, ~34 times less abundant than methanol (CH$_3$OH), and significantly higher than predicted by astrochemical models. Probable formation and destruction pathways are discussed, primarily through the reaction of the CH$_3$OH photodissociation products, the methoxy (CH$_3$O) and hydroxymethyl (CH$_2$OH) radicals. Finally, we comment on the implications of these mechanisms on gas-phase vs grain-surface routes operative in the region, and the possibility of electron-induced dissociation of CH$_3$OH rather than photodissociation., Comment: Accepted in Astrophysical Journal Letters

We report the first interstellar detection of DC$_7$N and six $^{13}$C-bearing isotopologues of HC$_7$N toward the dark cloud TMC-1 through observations with the Green Bank Telescope, and confirm the recent detection of HC$_5$$^{15}$N. For the average of the $^{13}$C isotopomers, DC$_7$N, and HC$_5$$^{15}$N, we derive column densities of 1.9(2)$\times$10$^{11}$, 2.5(9)$\times$10$^{11}$, and 1.5(4)$\times$10$^{11}$ cm$^{-2}$, respectively. The resulting isotopic ratios are consistent with previous values derived from similar species in the source, and we discuss the implications for the formation chemistry of the observed cyanopolyynes. Within our uncertainties, no significant $^{13}$C isotopomer variation is found for HC$_7$N, limiting the significance CN could have in its production. The results further show that, for all observed isotopes, HC$_5$N may be isotopically depleted relative to HC$_3$N and HC$_7$N, suggesting that reactions starting from smaller cyanopolyynes may not be efficient to form HC$_{n}$N. This leads to the conclusion that the dominant production route may be the reaction between hydrocarbon ions and nitrogen atoms., Comment: 8 pages, 2 figures, 3 tables, accepted to MNRAS

We report the detection of the carbon-chain radical HC$_5$O for the first time in the interstellar medium toward the dark cloud TMC-1 using the 100 m Green Bank Telescope. We observe four hyperfine components of this radical in the $J = 17/2 \rightarrow 15/2$ rotational transition that originates from the $^2\Pi_{1/2}$ fine structure level of its ground state, and calculate an abundance of $n/n_{H_2}$ = $1.7\times 10^{-10}$, assuming an excitation temperature of $T_{ex} = 7$~K. No indication of HC$_3$O, HC$_4$O, HC$_6$O, is found in these or archival observations of the source, while we report tentative evidence for HC$_7$O. We compare calculated upper limits, and the abundance of HC$_5$O to predictions based on (1) the abundance trend of the analogous HC$_n$N family in TMC-1 and (2) a gas-grain chemical model. We find that the gas-grain chemical model well reproduces the observed abundance of HC$_5$O, as well as the upper limits of HC$_3$O, HC$_6$O, and HC$_7$O, but HC$_4$O is over produced. The prospects for astronomical detection of both shorter and longer HC$_n$O chains are discussed., Comment: Accepted in The Astrophysical Journal Letters

Bell et al. (1997) reported the first detection of the cyanopolyyne HC$_{11}$N toward the cold dark cloud TMC-1; no subsequent detections have been reported toward any source. Additional observations of cyanopolyynes and other carbon-chain molecules toward TMC-1 have shown a log-linear trend between molecule size and column density, and in an effort to further explore the underlying chemical processes driving this trend, we have analyzed GBT observations of HC$_9$N and HC$_{11}$N toward TMC-1. Although we find an HC$_9$N column density consistent with previous values, HC$_{11}$N is not detected and we derive an upper limit column density significantly below that reported in Bell et al. Using a state-of-the-art chemical model, we have investigated possible explanations of non-linearity in the column density trend. Despite updating the chemical model to better account for ion-dipole interactions, we are not able to explain the non-detection of HC$_{11}$N, and we interpret this as evidence of previously unknown carbon-chain chemistry. We propose that cyclization reactions may be responsible for the depleted HC$_{11}$N abundance, and that products of these cyclization reactions should be investigated as candidate interstellar molecules., Comment: 10 pages, 7 figures, 3 tables, accepted for publication in MNRAS

The rotational spectra of thioisocyanic acid (HNCS), and its three energetic isomers (HSCN, HCNS, and HSNC) have been observed at high spectral resolution by a combination of chirped-pulse and Fabry-P\'{e}rot Fourier-transform microwave spectroscopy between 6 and 40~GHz in a pulsed-jet discharge expansion. Two isomers, thiofulminic acid (HCNS) and isothiofulminic acid (HSNC), calculated here to be 35-37~kcal/mol less stable than the ground state isomer HNCS, have been detected for the first time. Precise rotational, centrifugal distortion, and nitrogen hyperfine coupling constants have been determined for the normal and rare isotopic species of both molecules; all are in good agreement with theoretical predictions obtained at the coupled cluster level of theory. On the basis of isotopic spectroscopy, precise molecular structures have been derived for all four isomers by correcting experimental rotational constants for the effects of rotation-vibration calculated theoretically. Formation and isomerization pathways have also been investigated; the high abundance of HSCN relative to ground state HNCS, and the detection of strong lines of SH using CH$_3$CN and H$_2$S, suggest that HSCN is preferentially produced by the radical-radical reaction HS + CN. A radio astronomical search for HSCN and its isomers has been undertaken toward the high-mass star-forming region Sgr B2(N) in the Galactic Center with the 100 m Green Bank Telescope. While we find clear evidence for HSCN, only a tentative detection of HNCS is proposed, and there is no indication of HCNS or HSNC at the same rms noise level. HSCN, and tentatively HNCS, displays clear deviations from a single-excitation temperature model, suggesting weak masing may be occurring in some transitions in this source., Comment: Accepted in Physical Chemistry Chemical Physics

Life on Earth relies on chiral molecules, that is, species not superimposable on their mirror images. This manifests itself in the selection of a single molecular handedness, or homochirality, across the biosphere. We present the astronomical detection of a chiral molecule, propylene oxide (CH$_3$CHCH$_2$O), in absorption toward the Galactic Center. Propylene oxide is detected in the gas phase in a cold, extended molecular shell around the embedded, massive protostellar clusters in the Sagittarius B2 star-forming region. This material is representative of the earliest stage of solar system evolution in which a chiral molecule has been found.

L1157, a molecular dark cloud with an embedded Class 0 protostar possessing a bipolar outflow, is an excellent source for studying shock chemistry, including grain-surface chemistry prior to shocks, and post-shock, gas-phase processing. The L1157-B1 and B2 positions experienced shocks at an estimated ~2000 and 4000 years ago, respectively. Prior to these shock events, temperatures were too low for most complex organic molecules to undergo thermal desorption. Thus, the shocks should have liberated these molecules from the ice grain-surfaces en masse, evidenced by prior observations of SiO and multiple grain mantle species commonly associated with shocks. Grain species, such as OCS, CH3OH, and HNCO, all peak at different positions relative to species that are preferably formed in higher velocity shocks or repeatedly-shocked material, such as SiO and HCN. Here, we present high spatial resolution (~3") maps of CH3OH, HNCO, HCN, and HCO+ in the southern portion of the outflow containing B1 and B2, as observed with CARMA. The HNCO maps are the first interferometric observations of this species in L1157. The maps show distinct differences in the chemistry within the various shocked regions in L1157B. This is further supported through constraints of the molecular abundances using the non-LTE code RADEX (Van der Tak et al. 2007). We find the east/west chemical differentiation in C2 may be explained by the contrast of the shock's interaction with either cold, pristine material or warm, previously-shocked gas, as seen in enhanced HCN abundances. In addition, the enhancement of the HNCO abundance toward the the older shock, B2, suggests the importance of high-temperature O-chemistry in shocked regions., Comment: Accepted for publication in the Astrophysical Journal

A deep search for the potential glycine precursor hydroxylamine (NH$_2$OH) using the Caltech Submillimeter Observatory (CSO) at $\lambda = 1.3$ mm and the Combined Array for Research in Millimeter-wave Astronomy (CARMA) at $\lambda = 3$ mm is presented toward the molecular outflow L1157, targeting the B1 and B2 shocked regions. We report non-detections of NH$_2$OH in both sources. We a perform non-LTE analysis of CH$_3$OH observed in our CSO spectra to derive kinetic temperatures and densities in the shocked regions. Using these parameters, we derive upper limit column densities of NH$_2$OH of $\leq1.4 \times 10^{13}$~cm$^{-2}$ and $\leq1.5 \times 10^{13}$~cm$^{-2}$ toward the B1 and B2 shocks, respectively, and upper limit relative abundances of $N_{NH_2OH}/N_{H_2} \leq1.4 \times 10^{-8}$ and $\leq1.5 \times 10^{-8}$, respectively., Comment: Accepted in the Astrophysical Journal

We present a 30 - 50 GHz survey of Sagittarius B2(N) conducted with the Australia Telescope Compact Array (ATCA) with 5 - 10 arcsec resolution. This work releases the survey data and demonstrates the utility of scripts that perform automated spectral line fitting on broadband line data. We describe the line-fitting procedure, evaluate the performance of the method, and provide access to all data and scripts. The scripts are used to characterize the spectra at the positions of three HII regions, each with recombination line emission and molecular line absorption. Towards the most line-dense of the three regions characterised in this work, we detect ~500 spectral line components of which ~90 per cent are confidently assigned to H and He recombination lines and to 53 molecular species and their isotopologues. The data reveal extremely subthermally excited molecular gas absorbing against the continuum background at two primary velocity components. Based on the line radiation over the full spectra, the molecular abundances and line excitation in the absorbing components appear to vary substantially towards the different positions, possibly indicating that the two gas clouds are located proximate to the star forming cores instead of within the envelope of Sgr B2. Furthermore, the spatial distributions of species including CS, OCS, SiO, and HNCO indicate that the absorbing gas components likely have high UV-flux. Finally, the data contain line-of-sight absorption by $\sim$15 molecules observed in translucent gas in the Galactic Center, bar, and intervening spiral arm clouds, revealing the complex chemistry and clumpy structure of this gas. Formamide (NH$_2$CHO) is detected for the first time in a translucent cloud., Comment: 31 pages of the article, with 53 additional pages of appendices. 16 figures in the main article

Recently, Lattelais et al. (2009) have interpreted aggregated observations of molecular isomers to suggest that there exists a "minimum energy principle'', such that molecular formation will favor more stable molecular isomers for thermodynamic reasons. To test the predictive power of this principle, we have fully characterized the spectra of the three isomers of C$_{3}$H$_{2}$O toward the well known molecular region Sgr B2(N). Evidence for the detection of the isomers cyclopropenone (c-C$_{3}$H$_{2}$O) and propynal (HCCCHO) is presented, along with evidence for the non-detection of the lowest zero-point energy isomer, propadienone (CH$_2$CCO). We interpret these observations as evidence that chemical formation pathways, which may be under kinetic control, have a more pronounced effect on final isomer abundances than thermodynamic effects such as the minimum energy principle., Comment: Accepted for publication in ApJ, 11 pages, 6 figures