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Anthony J. Remijan

Publications and source records attributed to Anthony J. Remijan.

At least 37 records · Page 2Linked to original sources

Explaining the Chemical Inventory of Orion KL through Machine Learning

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).

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Low NH$_{3}$/H$_{2}$O ratio in comet C/2020 F3 (NEOWISE) at 0.7 au from the Sun

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 $3σ$ 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.

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Molecular Outgassing in Centaur 29P/Schwassmann-Wachmann 1 During Its Exceptional 2021 Outburst: Coordinated Multi-Wavelength Observations Using nFLASH at APEX and iSHELL at the NASA-IRTF

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.

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Investigating Anomalous Photochemistry in the Inner Wind of IRC+10216 Through Interferometric Observations of HC$_3$N

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.

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Discovery of Interstellar 2-Cyanoindene (2-C$_9$H$_7$CN) in GOTHAM Observations of TMC-1

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$σ$ 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.

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A Search for Heterocycles in GOTHAM Observations of TMC-1

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.

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CH3-Terminated Carbon Chains in the GOTHAM Survey of TMC-1: Evidence of Interstellar CH3C7N

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$σ$, 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.

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Leveraging the ALMA Atacama Compact Array for Cometary Science: An Interferometric Survey of Comet C/2015 ER61 (PanSTARRS) and Evidence for a Distributed Source of Carbon Monosulfide

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.

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Detection of Two Interstellar Polycyclic Aromatic Hydrocarbons via Spectral Matched Filtering

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.

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Rapidly Varying Anisotropic Methanol (CH$_3$OH) Production in the Inner Coma of Comet 46P/Wirtanen as Revealed by the ALMA Atacama Compact Array

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 ($<$2000 km from the nucleus) of 46P/Wirtanen approximately one week before its closest approach to Earth ($Δ$ = 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.

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Interstellar Detection of the Highly Polar Five-Membered Ring Cyanocyclopentadiene

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.

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Ubiquitous Aromatic Carbon Chemistry at the Earliest Stages of Star Formation

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.

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An Investigation of Spectral Line Stacking Techniques and Application to the Detection of HC$_{11}$N

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.

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Detection of Interstellar HC$_4$NC and an Investigation of Isocyanopolyyne Chemistry under TMC-1 Conditions

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 $10.5 σ$. 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.

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Early Science from GOTHAM: Project Overview, Methods, and the Detection of Interstellar Propargyl Cyanide (HCCCH$_2$CN) in TMC-1

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.

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The family of amide molecules toward NGC 6334I

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.

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A Search for Light Hydrides in the Envelopes of Evolved Stars

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.

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Searches for Interstellar HCCSH and H$_2$CCS

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.

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