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Abstract Spectral line surveys of the Taurus Molecular Cloud-1 (TMC-1) have led to the detection of more than 100 new molecular species, making it the most prolific source of interstellar molecular discoveries. These wide-band, high-sensitivity line surveys have been enabled by advances in telescope and receiver technology, particularly at centimeter and millimeter wavelengths. In this work, we present a statistical analysis of the molecular inventory of TMC-1 as probed by the GOTHAM large program survey from 3.9 to 36.4 GHz. To fully unlock the potential of the ∼29 GHz spectral bandwidth, we developed an automated pipeline for data reduction and calibration. We applied a Bayesian approach with Markov Chain Monte Carlo fitting to the calibrated spectra and constrained column densities for 102 molecular species detected in TMC-1, including 75 main isotopic species, 20 carbon-13 substituted species, and seven deuterium-substituted species. This list of the detected gas-phase molecules is populated by unsaturated hydrocarbons, in stark contrast to the oxygen-rich organics found in sublimated ices around protostars. Of note, 10 individual aromatic molecules were identified in the GOTHAM observations, contributing 0.011% of the gas-phase carbon budget probed by detected molecules when including CO and 6% when excluding CO. This work provides a reference set of observed gas-phase molecular abundances for interstellar clouds, offering a new benchmark for astrochemical theoretical models. 

Abstract We used new high spectral resolution observations of propynal (HCCCHO) toward 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 a 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 theJ= 2–1 and 3–2 transitions in the astronomical data, using a Markov Chain Monte Carlo analysis, a best fit to the total HCCCHO column density of ${7.28}_{-1.94}^{+4.08}\times {10}^{12}$cm⁻²was 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 comes online. 

Abstract We present the spectroscopic characterization of cyclopropenethione in the laboratory and detect it in space using the Green Bank Telescope Observations of TMC-1: Hunting Aromatic Molecules survey. The detection of this molecule—the missing link in understanding the C₃H₂S isomeric family in TMC-1—completes the detection of all three low-energy isomers of C₃H₂S, as both CH₂CCS and HCCCHS have been previously detected in this source. The total column density of this molecule (N_Tof $5.72_{-1.61}^{+2.65}\times 10^{10}$cm⁻²at an excitation temperature of $4.7_{-1.1}^{+1.3}$K) is smaller than both CH₂CCS and HCCCHS and follows nicely the relative dipole principle (RDP), a kinetic rule of thumb for predicting isomer abundances that suggests that, all other chemistry among a family of isomers being the same, the member with the smallest dipole (μ) should be the most abundant. The RDP now holds for the astronomical abundance ratios of both the S-bearing and O-bearing counterparts observed in TMC-1; however, CH₂CCO continues to elude detection in any astronomical source. 

Abstract We present the synthesis and laboratory rotational spectroscopy of the seven-ring polycyclic aromatic hydrocarbon (PAH) cyanocoronene (C₂₄H₁₁CN) using a laser-ablation-assisted cavity-enhanced Fourier transform microwave spectrometer. A total of 71 transitions were measured and assigned between 6.8 and 10.6 GHz. Using these assignments, we searched for emission from cyanocoronene in the Green Bank Telescope (GBT) Observations of TMC-1: Hunting Aromatic Molecules project observations of the cold dark molecular cloud TMC-1 using the 100 m GBT. We detect a number of individually resolved transitions in ultrasensitiveX-band observations and perform a Markov Chain Monte Carlo analysis to derive best-fit parameters, including a total column density of $N\left({\mathrm{C}}_{24}{\mathrm{H}}_{11}\mathrm{CN}\right)=2.69_{-0.23}^{+0.26}\times 10^{12}{\mathrm{cm}}^{-2}$at a temperature of $6.05_{-0.37}^{+0.38}$K. A spectral stacking and matched filtering analysis provides a robust 17.3σsignificance to the overall detection. The derived column density is comparable to that of cyano-substituted naphthalene, acenaphthylene, and pyrene, defying the trend of decreasing abundance with increasing molecular size and complexity found for carbon chains. We discuss the implications of the detection for our understanding of interstellar PAH chemistry and highlight major open questions and next steps. 

Polycyclic aromatic hydrocarbons (PAHs) are organic molecules containing adjacent aromatic rings. Infrared emission bands show that PAHs are abundant in space, but only a few specific PAHs have been detected in the interstellar medium. We detected 1-cyanopyrene, a cyano-substituted derivative of the related four-ring PAH pyrene, in radio observations of the dense cloud TMC-1, using the Green Bank Telescope. The measured column density of 1-cyanopyrene is $\sim \text{1}{\text{.52×10}}^{\text{12}}$cm⁻², from which we estimate that pyrene contains up to 0.1% of the carbon in TMC-1. This abundance indicates that interstellar PAH chemistry favors the production of pyrene. We suggest that some of the carbon supplied to young planetary systems is carried by PAHs that originate in cold molecular clouds. 

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. 

Abstract Theoretical models and observations suggest that the abundances of molecular ions in protoplanetary disks should be highly sensitive to the variable ionization conditions set by the young central star. We present a search for temporal flux variability of HCO⁺J= 1–0, which was observed as a part of the Molecules with Atacama Large Millimeter/submillimeter Array (ALMA) at Planet-forming Scales ALMA Large Program. We split out and imaged the line and continuum data for each individual day the five sources were observed (HD 163296, AS 209, GM Aur, MWC 480, and IM Lup, with between three and six unique visits per source). Significant enhancement (>3σ) was not observed, but we find variations in the spectral profiles in all five disks. Variations in AS 209, GM Aur, and HD 163296 are tentatively attributed to variations in HCO⁺flux, while variations in IM Lup and MWC 480 are most likely introduced by differences in theuvcoverage, which impact the amount of recovered flux during imaging. The tentative detections and low degree of variability are consistent with expectations of X-ray flare-driven HCO⁺variability, which requires relatively large flares to enhance the HCO⁺rotational emission at significant (>20%) levels. These findings also demonstrate the need for dedicated monitoring campaigns with high signal-to-noise ratios to fully characterize X-ray flare-driven chemistry. 

Abstract Using data from the Green Bank Telescope (GBT) Observations of TMC-1: Hunting for Aromatic Molecules (GOTHAM) survey, we report the first astronomical detection of the C 10 H − anion. The astronomical observations also provided the necessary data to refine the spectroscopic parameters of C 10 H − . From the velocity stacked data and the matched filter response, C 10 H − is detected at >9 σ confidence level at a column density of 4.04 − 2.23 + 10.67 × 10 11 cm −2 . A dedicated search for the C 10 H radical was also conducted toward TMC-1. In this case, the stacked molecular emission of C 10 H was detected at a ∼3.2 σ confidence interval at a column density of 2.02 − 0.82 + 2.68 × 10 11 cm −2 . However, as the determined confidence level is currently <5 σ , we consider the identification of C 10 H as tentative. The full GOTHAM data set was also used to better characterize the physical parameters including column density, excitation temperature, line width, and source size for the C 4 H, C 6 H, and C 8 H radicals and their respective anions, and the measured column densities were compared to the predictions from a gas/grain chemical formation model and from a machine learning analysis. Given the measured values, the C 10 H − /C 10 H column density ratio is ∼ 2.0 − 1.6 + 5.9 —the highest value measured between an anion and neutral species to date. Such a high ratio is at odds with current theories for interstellar anion chemistry. For the radical species, both models can reproduce the measured abundances found from the survey; however, the machine learning analysis matches the detected anion abundances much better than the gas/grain chemical model, suggesting that the current understanding of the formation chemistry of molecular anions is still highly uncertain. 

Abstract 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 ∼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 (CH 3 C 2 n H) and methylcyanopolyynes (CH 3 C 2 n -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 methylpolyyne and methylcyanopolyyne families exhibit stark differences from one another, pointing to separate interstellar formation pathways, which is confirmed through gas–grain chemical modeling with nautilus .