arXiv subjects

Eric R. Willis

Publications and source records attributed to Eric R. Willis.

15 recordsLinked to original sources

arXiv2024

Interstellar Glycolaldehyde, Methyl Formate, and Acetic Acid. II. Chemical Modeling of the Bimodal Abundance Pattern in NGC 6334I

Gas-phase abundance ratios between \ce{C2H4O2} isomers methyl formate (MF), glycolaldehyde (GA), and acetic acid (AA) are typically on the order of 100:10:1 in star-forming regions. However, an unexplained divergence from this neat relationship was recently observed towards a collection of sources in the massive protocluster NGC 6334I; some sources exhibited extreme MF:GA ratios, producing a bimodal behavior between different sources, while the MF:AA ratio remained stable. Here, we use a three-phase gas-grain hot-core chemical model to study the effects of a large parameter space on the simulated \ce{C2H4O2} abundances. A combination of high gas densities and long timescales during ice-mantle desorption ($\sim$125--160~K) appears to be the physical cause of the high MF:GA ratios. The main chemical mechanism for GA destruction occurring under these conditions is the rapid adsorption and reaction of atomic H with GA on the ice surfaces before it has time to desorb. The different binding energies of MF and GA on water ice are crucial to the selectivity of the surface destruction mechanism; individual MF molecules rapidly escape the surface when exposed by water loss, while GA lingers and is destroyed by H. Moderately elevated cosmic-ray ionization rates can increase absolute levels of COM production in the ices and increase the MF:GA ratio, but extreme values are destructive for gas-phase COMs. We speculate that the high densities required for extreme MF:GA ratios could be evidence of COM emission dominated by COMs desorbing within a circumstellar disk.

astro-ph.GA↗

arXiv2024

Ice Chemistry Modeling of Active Phase Comets: Hale-Bopp

We present a chemical kinetics model of the solid-phase chemical evolution of a comet, beginning with a long period of cold-storage in the Oort Cloud, followed by five orbits that bring the comet close to the Sun. The chemical model is based on an earlier treatment that considered only the cold-storage phase, and which was based on the interstellar ice chemical kinetics model MAGICKAL. The comet is treated as 25 chemically distinct layers. Updates to the previous model includes: (i) Time- and depth-dependent temperature profiles according to heliocentric distance; (ii) a rigorous treatment of back-diffusion for species capable of diffusing through the bulk-ice layers; (iii) adoption of recent improvements in the kinetic treatment of nondiffusive chemical reaction rates. Starting from an initially simple ice composition, interstellar UV photons drive a rapid chemistry in the upper micron of material, but diminished by absorption of the UV by the dust component. Galactic cosmic rays (GCRs) drive a much slower chemistry in the deeper ices over the long cold-storage period down to 10 m. The first solar approach drives off the upper layers of ice material via thermal desorption and/or dissociation, bringing closer to the surface the deeper material that previously underwent long-term processing by GCRs. Subsequent orbits are more uniform in their chemical behavior. Loss of molecular material leads to concentration of the dust in the upper layers. Substantial quantities of complex organic molecules are formed in the upper 10 m during the cold storage phase, with some of this material released during solar approach; however, their abundances with respect to water appear too low to account for the observed gas-phase values for comet Hale-Bopp, indicating that the majority of complex molecular material observed, at least in comet Hale-Bopp, is an inheritance of primordial material.

astro-ph.EP↗

arXiv2021

Formation of complex organic molecules in hot molecular cores through nondiffusive grain-surface and ice-mantle chemistry

A new, more comprehensive model of gas-grain chemistry in hot molecular cores is presented, in which nondiffusive reaction processes on dust-grain surfaces and in ice mantles are implemented alongside traditional diffusive surface/bulk-ice chemistry. We build on our nondiffusive treatments used for chemistry in cold sources, adopting a standard collapse/warm-up physical model for hot cores. A number of other new chemical model inputs and treatments are also explored in depth, culminating in a final model that demonstrates excellent agreement with gas-phase observational abundances for many molecules, including some (e.g. methoxymethanol) that could not be reproduced by conventional diffusive mechanisms. Observed ratios of structural isomers methyl formate, glycolaldehyde and acetic acid are well reproduced by the models. The main temperature regimes are identified in which various complex organic molecules (COMs) are formed. Nondiffusive chemistry advances the production of many COMs to much earlier times and lower temperatures than in previous model implementations. Those species may form either as by-products of simple-ice production, or via early photochemistry within the ices while external UV photons can still penetrate. Cosmic ray-induced photochemistry is less important than in past models, although it affects some species strongly over long timescales. Another production regime occurs during the high-temperature desorption of solid water, whereby radicals trapped in the ice are released onto the grain/ice surface, where they rapidly react. Several recently-proposed gas-phase COM-production mechanisms are also introduced, but they rarely dominate. New surface/ice reactions involving CH and CH$_2$ are found to contribute substantially to the formation of certain COMs.

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↗

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

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↗

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

Interstellar Glycolaldehyde, Methyl Formate, and Acetic Acid I: A Bi-modal Abundance Pattern in Star Forming Regions

The relative column densities of the structural isomers methyl formate, glycolaldehyde, and acetic acid are derived for a dozen positions towards the massive star-forming regions MM1 and MM2 in the NGC 6334I complex, which are separated by $\sim$4000 AU. Relative column densities of these molecules are also gathered from the literature for 13 other star-forming regions. In this combined dataset, a clear bi-modal distribution is observed in the relative column densities of glycolaldehyde and methyl formate. No such distribution is evident with acetic acid. The two trends are comprised of star-forming regions with a variety of masses, suggesting that there must be some other common parameter that is heavily impacting the formation of glycolaldehyde. This is indicative of some demonstrable differentiation in these cores; studying the abundances of these isomers may provide a clue as to the integral chemical processes ongoing in a variety of protostellar environments.

astro-ph.GA↗

arXiv2018

Science with an ngVLA: Observing the Effects of Chemistry on Exoplanets and Planet Formation

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.

astro-ph.EP↗

arXiv2018

First Results of an ALMA Band 10 Spectral Line Survey of NGC 6334I: Detections of Glycolaldehyde (HC(O)CH$_2$OH) and a New Compact Bipolar Outflow in HDO and CS

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.

astro-ph.GA↗

arXiv2017

ALMA Detection of Interstellar Methoxymethanol (CH$_3$OCH$_2$OH)

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.

astro-ph.GA↗

arXiv2017

Kinetic Monte Carlo simulations of the grain-surface back-diffusion effect

Back-diffusion is the phenomenon by which random walkers revisit binding sites on a lattice. This phenomenon must occur on interstellar dust particles, slowing down dust-grain reactions, but it is not accounted for by standard rate-equation models. Microscopic kinetic Monte Carlo models have been used to investigate the effect of back-diffusion on reaction rates on interstellar dust grains. Grain morphology, size, and grain-surface coverage were varied and the effects of these variations on the magnitude of the back-diffusion effect were studied for the simple H+H reaction system. This back-diffusion effect is seen to reduce reaction rates by a maximum factor of ~5 for the canonical grain of 10$^6$ binding sites.The resulting data were fit to logarithmic functions that can be used to reproduce the effects of back-diffusion in rate-equation models.

astro-ph.GA↗

arXiv2017

Kinetic Monte Carlo simulations of the grain-surface back-diffusion effect

Rate-equation models are a widely-used and inexpensive tool for the simulation of interstellar chemistry under a range of physical conditions. However, their application to grain-surface chemical systems necessitates a number of simplifying assumptions, due to the requirement to treat only the total population of each species, using averaged rates, rather than treating each surface particle as an independent entity. While the outputs from rate-equation models are strictly limited to such population information, the inputs -- in the form of the averaged rates that control the time-evolution of chemical populations -- can be guided by the results from more exact simulation methods. Here, we examine the effects of back-diffusion, wherein particles diffusing on a surface revisit binding sites on the lattice, slowing the total reaction rate. While this effect has been studied for two-particle systems, its influence at greater surface coverage of reactants has not been explored. Results from two Monte Carlo kinetics models (one a 2-D periodic lattice, the other the surface of a three dimensionally-realized grain) were used to develop a means to incorporate the grain-surface back-diffusion effect into rate-equation methods. The effects of grain size, grain morphology, and surface coverage on the magnitude of the back-diffusion effect were studied for the simple H+H reaction system. The results were fit with expressions that can be easily incorporated into astrochemical rate-equation models to reproduce accurately the effects of back-diffusion on grain-surface reaction rates. Back-diffusion reduces reaction rates by a maximum factor of around 5 for the canonical grain of $\sim$10$^6$ surface sites, but this falls to unity at close to full surface coverage.

astro-ph.GA↗