arXiv subjects

Kin Long Kelvin Lee

Publications and source records attributed to Kin Long Kelvin Lee.

At least 37 records · Page 2Linked to original sources

arXiv2022

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.

astro-ph.GA↗

arXiv2022

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.

astro-ph.GA↗

arXiv2021

Machine Learning of Interstellar Chemical Inventories

The characterization of interstellar chemical inventories provides valuable insight into the chemical and physical processes in astrophysical sources. The discovery of new interstellar molecules becomes increasingly difficult as the number of viable species grows combinatorially, even when considering only the most thermodynamically stable. In this work, we present a novel approach for understanding and modeling interstellar chemical inventories by combining methodologies from cheminformatics and machine learning. Using multidimensional vector representations of molecules obtained through unsupervised machine learning, we show that identification of candidates for astrochemical study can be achieved through quantitative measures of chemical similarity in this vector space, highlighting molecules that are most similar to those already known in the interstellar medium. Furthermore, we show that simple, supervised learning regressors are capable of reproducing the abundances of entire chemical inventories, and predict the abundance of not yet seen molecules. As a proof-of-concept, we have developed and applied this discovery pipeline to the chemical inventory of a well-known dark molecular cloud, the Taurus Molecular Cloud 1 (TMC-1); one of the most chemically rich regions of space known to date. In this paper, we discuss the implications and new insights machine learning explorations of chemical space can provide in astrochemistry.

astro-ph.GA↗

arXiv2021

Discovery of the Pure Polycyclic Aromatic Hydrocarbon Indene ($c$-C$_9$H$_8$) with GOTHAM Observations of TMC-1

Polycyclic Aromatic Hydrocarbons (PAHs) have long been invoked in the study of interstellar and protostellar sources, but the unambiguous identification of any individual PAH has proven elusive until very recently. As a result, the formation mechanisms for this important class of molecules remain poorly constrained. Here we report the first interstellar detection of a pure hydrocarbon PAH, indene (C$_9$H$_8$), as part of the GBT Observations of TMC-1: Hunting for Aromatic Molecules (GOTHAM) survey. This detection provides a new avenue for chemical inquiry, complementing the existing detections of CN-functionalized aromatic molecules. From fitting the GOTHAM observations, indene is found to be the most abundant organic ring detected in TMC-1 to date. And from astrochemical modeling with NAUTILUS, the observed abundance is greater than the model's prediction by several orders of magnitude suggesting that current formation pathways in astrochemical models are incomplete. The detection of indene in relatively high abundance implies related species such as cyanoindene, cyclopentadiene, toluene, and styrene may be detectable in dark clouds.

astro-ph.GA↗

arXiv2021

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.

astro-ph.GA↗

arXiv2021

Interstellar Detection of 2-Cyanocyclopentadiene, C$_5$H$_5$CN, a Second Five-Membered Ring Toward TMC-1

Using radio observations with the Green Bank Telescope, evidence has now been found for a second five-membered ring in the dense cloud Taurus Molecular Cloud-1 (TMC-1). Based on additional observations of an ongoing, large-scale, high-sensitivity spectral line survey (GOTHAM) at centimeter wavelengths toward this source, we have used a combination of spectral stacking, Markov chain Monte Carlo (MCMC), and matched filtering techniques to detect 2-cyanocyclopentadiene, a low-lying isomer of 1-cyanocyclopentadiene, which was recently discovered there by the same methods. The new observational data also yields a considerably improved detection significance for the more stable isomer and evidence for several individual transitions between 23 - 32 GHz. Through our MCMC analysis, we derive total column densities of $8.3\times10^{11}$ and $1.9\times10^{11}$ cm$^{-2}$ for 1- and 2-cyanocyclopentadiene respectively, corresponding to a ratio of 4.4(6) favoring the former. The derived abundance ratios point towards a common formation pathway - most likely being cyanation of cyclopentadiene by analogy to benzonitrile.

astro-ph.GA↗

arXiv2021

Discovery of Interstellar trans-cyanovinylacetylene (HCCCH=CHCN) and vinylcyanoacetylene (H$_2$C=CHC$_3$N) in GOTHAM Observations of TMC-1

We report the discovery of two unsaturated organic species, trans-(E)-cyanovinylacetylene and vinylcyanoacetylene, using the second data release of the GOTHAM deep survey towards 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 (${\sim}$3$σ$). From this analysis, we derive column densities of $2\times10^{11}$ and $3\times10^{11}$ cm$^{-2}$ for vinylcyanoacetylene and trans-(E)-cyanovinylacetylene, respectively, and an upper limit of $<2\times10^{11}$ cm$^{-2}$ for trans-(Z)-cyanovinylacetylene. Comparisons with G3//B3LYP semi-empirical 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 discussion into how these species may be formed in TMC-1, with reference to related species like vinyl cyanide (CH$_2$=CHCN). As part of this discussion, we performed the same analysis for ethyl cyanide (CH$_3$CH$_2$CN), the hydrogenation product of CH$_2$=CHCN. This analysis provides evidence -- at 4.17$σ$ significance -- an upper limit to the column density of $<4\times10^{11}$ cm$^{-2}$; an order of magnitude lower than previous upper limits towards this source.

astro-ph.GA↗

arXiv2021

A rotational and vibrational investigation of phenylpropiolonitrile (C$_6$H$_5$C$_3$N)

The evidence for benzonitrile (C$_6$H$_5$CN}) in the starless cloud core TMC-1 makes high-resolution studies of other aromatic nitriles and their ring-chain derivatives especially timely. One such species is phenylpropiolonitrile (3-phenyl-2-propynenitrile, C$_6$H$_5$C$_3$N), whose spectroscopic characterization is reported here for the first time. The low resolution (0.5 cm$^{-1}$) vibrational spectrum of C$_6$H$_5$C$_3$N} has been recorded at far- and mid-infrared wavelengths (50 - 3500 cm$^{-1}$) using a Fourier Transform interferometer, allowing for the assignment of band centers of 14 fundamental vibrational bands. The pure rotational spectrum of the species has been investigated using a chirped-pulse Fourier transform microwave (FTMW) spectrometer (6 - 18 GHz), a cavity enhanced FTMW instrument (6 - 20 GHz), and a millimeter-wave one (75 - 100 GHz, 140 - 214 GHz). Through the assignment of more than 6200 lines, accurate ground state spectroscopic constants (rotational, centrifugal distortion up to octics, and nuclear quadrupole hyperfine constants) have been derived from our measurements, with a plausible prediction of the weaker bands through calculations. Interstellar searches for this highly polar species can now be undertaken with confidence since the astronomically most interesting radio lines have either been measured or can be calculated to very high accuracy below 300 GHz.

astro-ph.GA↗

arXiv2020

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.

astro-ph.GA↗

arXiv2020

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.

astro-ph.GA↗

arXiv2020

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.

astro-ph.GA↗

arXiv2020

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.

astro-ph.GA↗

arXiv2020

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.

astro-ph.GA↗

arXiv2020

Molecule Identification with Rotational Spectroscopy and Probabilistic Deep Learning

A proof-of-concept framework for identifying molecules of unknown elemental composition and structure using experimental rotational data and probabilistic deep learning is presented. Using a minimal set of input data determined experimentally, we describe four neural network architectures that yield information to assist in the identification of an unknown molecule. The first architecture translates spectroscopic parameters into Coulomb matrix eigenspectra, as a method of recovering chemical and structural information encoded in the rotational spectrum. The eigenspectrum is subsequently used by three deep learning networks to constrain the range of stoichiometries, generate SMILES strings, and predict the most likely functional groups present in the molecule. In each model, we utilize dropout layers as an approximation to Bayesian sampling, which subsequently generates probabilistic predictions from otherwise deterministic models. These models are trained on a modestly sized theoretical dataset comprising ${\sim}$83,000 unique organic molecules (between 18 and 180 amu) optimized at the $ω$B97X-D/6-31+G(d) level of theory where the theoretical uncertainty of the spectroscopic constants are well understood and used to further augment training. Since chemical and structural properties depend highly on molecular composition, we divided the dataset into four groups corresponding to pure hydrocarbons, oxygen-bearing, nitrogen-bearing, and both oxygen- and nitrogen-bearing species, training each type of network with one of these categories thus creating "experts" within each domain of molecules. We demonstrate how these models can then be used for practical inference on four molecules, and discuss both the strengths and shortcomings of our approach, and the future directions these architectures can take.

physics.chem-ph↗

arXiv2019

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.

astro-ph.GA↗

arXiv2019

Submillimeter spectroscopy and astronomical searches of vinyl mercaptan, C$_2$H$_3$SH

We have extended the pure rotational investigation of the two isomers syn and anti vinyl mercaptan to the millimeter domain using a frequency-multiplication spectrometer. The species were produced by a radiofrequency discharge in 1,2-ethanedithiol. Additional transitions have been re-measured in the centimeter band using Fourier-transform microwave spectroscopy to better determine rest frequencies of transitions with low-$J$ and low-$K_a$ values. Experimental investigations were supported by quantum chemical calculations on the energetics of both the [C$_2$,H$_4$,S] and [C$_2$,H$_4$,O] isomeric families. Interstellar searches for both syn and anti vinyl mercaptan as well as vinyl alcohol were performed in the EMoCA (Exploring Molecular Complexity with ALMA) spectral line survey carried out toward Sagittarius (Sgr) B2(N2) with the Atacama Large Millimeter/submillimeter Array (ALMA). Highly accurate experimental frequencies (to better than 100 kHz accuracy) for both syn and anti isomers of vinyl mercaptan have been measured up to 250 GHz; these deviate considerably from predictions based on extrapolation of previous microwave measurements. Reliable frequency predictions of the astronomically most interesting millimeter-wave lines for these two species can now be derived from the best-fit spectroscopic constants. From the energetic investigations, the four lowest singlet isomers of the [C$_2$,H$_4$,S] family are calculated to be nearly isoenergetic, which makes this family a fairly unique test bed for assessing possible reaction pathways. Upper limits for the column density of syn and anti vinyl mercaptan are derived toward the extremely molecule-rich star-forming region Sgr B2(N2) enabling comparison with selected complex organic molecules.

astro-ph.GA↗

arXiv2018

Gas phase detection and rotational spectroscopy of ethynethiol, HCCSH

We report the gas-phase detection and spectroscopic characterization of ethynethiol ($\mathrm{HCCSH}$), a metastable isomer of thioketene ($\mathrm{H_2C_2S}$) using a combination of Fourier-transform microwave and submillimeter-wave spectroscopies. Several $a$-type transitions of the normal species were initially detected below 40 GHz using a supersonic expansion-electrical discharge source, and subsequent measurement of higher-frequency, $b$-type lines using double resonance provided accurate predictions in the submillimeter region. With these, searches using a millimeter-wave absorption spectrometer equipped with a radio frequency discharge source were conducted in the range 280 - 660 GHz, ultimately yielding nearly 100 transitions up to $^rR_0(36)$ and $^rQ_0(68)$. From the combined data set, all three rotational constants and centrifugal distortion terms up to the sextic order were determined to high accuracy, providing a reliable set of frequency predictions to the lower end of the THz band. Isotopic substitution has enabled both a determination of the molecular structure of $\mathrm{HCCSH}$ and, by inference, its formation pathway in our nozzle discharge source via the bimolecular radical-radical recombination reaction $\mathrm{SH + C_2H}$, which is calculated to be highly exothermic (-477 kJ/mol) using the HEAT345(Q) thermochemical scheme.

astro-ph.GA↗

arXiv2018

HSCO$^+$ and DSCO$^+$: a multi-technique approach in the laboratory for the spectroscopy of interstellar ions

Protonated molecular species have been proven to be abundant in the interstellar gas. This class of molecules is also pivotal for the determination of important physical parameters for the ISM evolution (e.g. gas ionisation fraction) or as tracers of non-polar, hence not directly observable, species. The identification of these molecular species through radioastronomical observations is directly linked to a precise laboratory spectral characterisation. The goal of the present work is to extend the laboratory measurements of the pure rotational spectrum of the ground electronic state of protonated carbonyl sulfide (HSCO$^+$) and its deuterium substituted isotopomer (DSCO$^+$). At the same time, we show how implementing different laboratory techniques allows the determination of different spectroscopical properties of asymmetric-top protonated species. Three different high-resolution experiments were involved to detected for the first time the $b-$type rotational spectrum of HSCO$^+$, and to extend, well into the sub-millimeter region, the $a-$type spectrum of the same molecular species and DSCO$^+$. The electronic ground-state of both ions have been investigated in the 273-405 GHz frequency range, allowing the detection of 60 and 50 new rotational transitions for HSCO$^+$ and DSCO$^+$, respectively. The combination of our new measurements with the three rotational transitions previously observed in the microwave region permits the rest frequencies of the astronomically most relevant transitions to be predicted to better than 100 kHz for both HSCO$^+$ and DSCO$^+$ up to 500 GHz, equivalent to better than 60 m/s in terms of equivalent radial velocity. The present work illustrates the importance of using different laboratory techniques to spectroscopically characterise a protonated species at high frequency, and how a similar approach can be adopted when dealing with reactive species.

astro-ph.GA↗