We present an overview of the 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-C6H5CN) 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 (HCCCH2CN) 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.
We report an astronomical detection of HC4NC 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 . The ...total column density and excitation temperature of HC4NC are determined to be cm−2 and , respectively, using Markov chain Monte Carlo analysis. In addition to HC4NC, HCCNC is distinctly detected whereas no clear detection of HC6NC is made. We propose that the dissociative recombination of the protonated cyanopolyyne, HC5NH+, and the protonated isocyanopolyyne, HC4NCH+, are the main formation mechanisms for HC4NC while its destruction is dominated by reactions with simple ions and atomic carbon. With the proposed chemical networks, the observed abundances of HC4NC and HCCNC are reproduced satisfactorily.
Following the recent discovery of T-shaped GeC2, rotational spectra of three larger Ge carbides, linear GeC4, GeC5, and GeC6 have been observed using chirped pulse and cavity Fourier transform ...microwave spectroscopy and a laser ablation molecule source, guided by new high-level quantum chemical calculations of their molecular structure. Like their isovalent Si-bearing counterparts, Ge carbides with an even number of carbon atoms beyond GeC2 are predicted to possess 1Σ ground electronic states, while odd-numbered carbon chains are generally 3Σ; all are predicted to be highly polar. For the three new molecules detected in this work, rotational lines of four of the five naturally occurring Ge isotopic variants have been observed between 6 and 22 GHz. Combining these measurements with ab initio force fields, the Ge–C bond lengths have been determined to high precision: the derived values of 1.776 Å for GeC4, 1.818 Å for GeC5, and 1.782 Å for GeC6 indicate a double bond between these two atoms. Somewhat surprisingly, the spectrum of GeC5 very closely resembles that of a 1Σ molecule, implying a spin–spin coupling constant λ in excess of 770 GHz for this radical, a likely consequence of the large spin–orbit constant of atomic Ge (∼1000 cm−1). A systematic comparison between the production of SiCn and GeCn chains by laser ablation has also been undertaken. The present work suggests that other large metal-bearing molecules may be amenable to detection by similar means.
Abstract
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 ...and 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, 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 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.
Abstract
We report the discovery of two unsaturated organic species,
trans
-(E)-cyanovinylacetylene and vinylcyanoacetylene, using the second data release of the GOTHAM deep survey toward TMC-1 with ...the 100 m Green Bank Telescope. For both detections, we performed velocity stacking and matched filter analyses using Markov Chain Monte Carlo simulations, and for
trans
-(E)-cyanovinylacetylene, three rotational lines were observed at low signal-to-noise (∼3
σ
). From this analysis, we derive column densities of 2 × 10
11
and 3 × 10
11
cm
−2
for vinylcyanoacetylene and
trans
-(E)-cyanovinylacetylene, respectively, and an upper limit of <2 × 10
11
cm
−2
for
trans
-(Z)-cyanovinylacetylene. Comparisons with G3//B3LYP semiempirical thermochemical calculations indicate abundances of the H
3
C
5
N isomers are not consistent with their thermodynamic stability, and instead their abundances are mainly driven by dynamics. We provide a discussion on how these species may be formed in TMC-1, with reference to related molecules like vinyl cyanide (CH
2
= CHC ≡ N). As part of this discussion, we performed the same analysis for ethyl cyanide (CH
3
CH
2
C ≡ N), the hydrogenation product of CH
2
= CHC ≡ N. This analysis provides evidence—at 4.
2σ
significance—of an upper limit to the column density of <4 × 10
11
cm
−2
; an order of magnitude lower than previous upper limits toward this source.
Using chirped and cavity microwave spectroscopies, automated double resonance, new high-speed fitting and deep learning algorithms, and large databases of computed structures, the discharge products ...of benzene alone, or in combination with molecular oxygen or nitrogen, have been exhaustively characterized between 6.5 and 26 GHz. In total, more than 3300 spectral features were observed; 89% of these, accounting for 97% of the total intensity, have now been assigned to 152 distinct chemical species and 60 of their variants (i.e., isotopic species and vibrationally excited states). Roughly 50 of the products are entirely new or poorly characterized at high resolution, including many heavier by mass than the precursor benzene. These findings provide direct evidence for a rich architecture of two- and three-dimensional carbon and indicate that benzene growth, particularly the formation of ring–chain molecules, occurs facilely under our experimental conditions. The present analysis also illustrates the utility of microwave spectroscopy as a precision tool for complex mixture analysis, irrespective of whether the rotational spectrum of a product species is known a priori or not. From this large quantity of data, for example, it is possible to determine with confidence the relative abundances of different product masses, but more importantly the relative abundances of different isomers with the same mass. The complementary nature of this type of analysis to traditional mass spectrometry is discussed.
Atmospheric aerosols are large clusters of molecules and particulate matter that profoundly affect the Earth's radiation budget and climate. Gas-phase oxidation of volatile organic compounds is ...thought to play a key role in nucleation and aerosol growth, but remains poorly understood. One reaction proposed to trigger formation of condensable, low volatility organic compounds is that between Criegee intermediates and carboxylic acids to yield hydroperoxide esters. Here we isolate in high yield the simplest hydroperoxide ester, hydroperoxymethyl formate (HOOCH
2
OCHO), as a secondary product in the ozonolysis of ethylene, and establish by rotational spectroscopy that this ester adopts a nearly-rigid cyclic structure owing to a strong hydrogen bond between the peroxy hydrogen and carbonyl oxygen. Subsequent detection of this ester in the ozonolysis of propylene and isoprene suggests that terminal alkenes readily undergo specific types of second-order oxidation reactions that have been implicated in the formation of atmospheric aerosols.
Atmospheric aerosols are large clusters of molecules and particulate matter that profoundly affect the Earth's radiation budget and climate.
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 C10H− anion. The astronomical ...observations also provided the necessary data to refine the spectroscopic parameters of C10H−. From the velocity stacked data and the matched filter response, C10H− is detected at >9σ confidence level at a column density of 4.04−2.23+10.67×1011 cm−2. A dedicated search for the C10H radical was also conducted toward TMC-1. In this case, the stacked molecular emission of C10H was detected at a ∼3.2σ confidence interval at a column density of 2.02−0.82+2.68×1011 cm−2. However, as the determined confidence level is currently <5σ, we consider the identification of C10H 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 C4H, C6H, and C8H 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 C10H−/C10H 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.
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