arXiv subjects

Eric Herbst

Publications and source records attributed to Eric Herbst.

At least 55 records · Page 3Linked to original sources

arXiv2020

Theoretical kinetic studies of Venus chemistry. Formation and destruction of SCl, SCl2, and HSCl

Accurate and thorough characterization of the chemistry of compounds containing the third-row elements sulfur and chlorine is critical for modeling the composition of the atmosphere of Venus. We have used a combination of ab initio quantum chemistry and kinetic theory to characterize a group of nine exothermic reactions that involve the exotic sulfur-chlorine species SCl, SCl2, and HSCl, which are thought to be present in trace quantities in the atmosphere of Venus and are included to various degrees in the published atmospheric models. Reaction pathways were characterized with coupled cluster theory at the RCCSD(T) level with triple zeta quality correlation consistent basis sets. For reactions with barriers that lie above the reactant asymptote, the barrier height was extrapolated to the RCCSD(T) complete basis set level via single-point calculations with quadruple and quintuple zeta quality sets. Rate coefficients were predicted with capture theory and transition state theory as appropriate. We have found that in some cases addition-elimination reactions can compete with abstraction reactions due to the tendency of sulfur to form hypervalent compounds and intermediates via recoupled pair bonding.

physics.chem-ph↗

arXiv2020

The Role of Radiolysis in the Modelling of C$_{2}$H$_{4}$O$_{2}$ Isomers and Dimethyl Ether in Cold Dark Clouds

Complex organic molecules (COMs) have been detected in a variety of interstellar sources. The abundances of these COMs in warming sources can be explained by syntheses linked to increasing temperatures and densities, allowing quasi-thermal chemical reactions to occur rapidly enough to produce observable amounts of COMs, both in the gas phase, and upon dust grain ice mantles. The COMs produced on grains then become gaseous as the temperature increases sufficiently to allow their thermal desorption. The recent observation of gaseous COMs in cold sources has not been fully explained by these gas-phase and dust grain production routes. Radiolysis chemistry is a possible non-thermal method of producing COMs in cold dark clouds. This new method greatly increases the modeled abundance of selected COMs upon the ice surface and within the ice mantle due to excitation and ionization events from cosmic ray bombardment. We examine the effect of radiolysis on three C$_{2}$H$_{4}$O$_{2}$ isomers -- methyl formate (HCOOCH$_3$), glycolaldehyde (HCOCH$_2$OH), and acetic acid (CH$_3$COOH) -- and a chemically similar molecule, dimethyl ether (CH$_3$OCH$_3$), in cold dark clouds. We then compare our modelled gaseous abundances with observed abundances in TMC-1, L1689B, and B1-b.

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

The First Mid-Infrared Detection of HNC in the Interstellar Medium: Probing the Extreme Environment Towards the Orion Hot Core

We present the first mid-infrared (MIR) detections of HNC and H13CN in the interstellar medium, and numerous, resolved HCN rovibrational transitions. Our observations span 12.8 to 22.9 micron towards the hot core Orion IRc2, obtained with the Echelon-Cross-Echelle Spectrograph aboard the Stratospheric Observatory for Infrared Astronomy (SOFIA). Exceptional, ~5 km/s, resolution distinguishes individual rovibrational transitions of the HNC and HCN P, Q, and R branches; and the H13CN R branch. This allows direct measurement of the species' excitation temperatures, column densities, and relative abundances. HNC and H13CN exhibit a local standard rest velocity of -7 km/s that may be associated with an outflow from nearby radio source I and an excitation temperature of about 100 K. We resolve two velocity components for HCN, the primary component also being at -7 km/s with temperature 165 K. The hottest component, which had never before been observed, is at 1 km/s with temperature 309 K. This is the closest component to the hot core's centre measured to date. The derived 12C/13C=13 is below expectation for Orion's Galactocentric distance, but the derived HCN/HNC=72 is expected for this extreme environment. Compared to previous sub-mm and mm observations, our SOFIA line survey of this region shows that the resolved MIR molecular transitions are probing a distinct physical component and isolating the chemistry closest to the hot core.

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

Investigation of Chemical Differentiation among the NGC2264 Cluster-Forming Clumps

We have carried out mapping observations of molecular emission lines of HC$_{3}$N and CH$_{3}$OH toward two massive cluster-forming clumps, NGC2264-C and NGC2264-D, using the Nobeyama 45-m radio telescope. We derive an $I$(HC$_{3}$N)/$I$(CH$_{3}$OH) integrated intensity ratio map, showing a higher value at clumps including 2MASS point sources at the northern part of NGC2264-D. Possible interpretations of the $I$(HC$_{3}$N)/$I$(CH$_{3}$OH) ratio are discussed. We have also observed molecular emission lines from CCS and N$_{2}$H$^{+}$ toward five positions in each clump. We investigate the $N$(N$_{2}$H$^{+}$)/$N$(CCS) and $N$(N$_{2}$H$^{+}$)/$N$(HC$_{3}$N) column density ratios among the ten positions in order to test whether they can be used as chemical evolutionary indicators in these clumps. The $N$(N$_{2}$H$^{+}$)/$N$(CCS) ratio shows a very high value toward a bright embedded IR source (IRS1), whereas the $N$(N$_{2}$H$^{+}$)/$N$(HC$_{3}$N) ratio at IRS1 is comparable with those at the other positions. These results suggest that UV radiation affects the chemistry around IRS1. We find that there are positive correlations between these column density ratios and the excitation temperatures of N$_{2}$H$^{+}$, which implies the chemical evolution of clumps. These chemical evolutionary indicators likely reflect the combination of evolution along the filamentary structure and evolution of each clump.

astro-ph.GA↗

arXiv2019

Efficient Production of S$_8$ in Interstellar Ices: The effects of cosmic ray-driven radiation chemistry and non-diffusive bulk reactions

In this work, we reexamine sulfur chemistry occurring on and in the ice mantles of interstellar dust grains, and report the effects of two new modifications to standard astrochemical models; namely, (a) the incorporation of cosmic ray-driven radiation chemistry and (b) the assumption of fast, non-diffusive reactions for key radicals in the bulk. Results from our models of dense molecular clouds show that these changes can have a profound influence on the abundances of sulfur-bearing species in ice mantles, including a reduction in the abundance of solid-phase H$_2$S and HS, and a significant increase in the abundances of OCS, SO$_2$, as well as pure allotropes of sulfur, especially S$_8$. These pure-sulfur species - though nearly impossible to observe directly - have long been speculated to be potential sulfur reservoirs and our results represent possibly the most accurate estimates yet of their abundances in the dense ISM. Moreover, the results of these updated models are found to be in good agreement with available observational data. Finally, we examine the implications of our findings with regard to the as-yet-unknown sulfur reservoir thought to exist in dense interstellar environments.

astro-ph.GA↗

arXiv2019

$^{13}$C Isotopic Fractionation of CCH in Two Starless Cores: L1521B and L134N

We have carried out observations of CCH and its two $^{13}$C isotopologues, $^{13}$CCH and C$^{13}$CH, in the 84 - 88 GHz band toward two starless cores, L1521B and L134N (L183), using the Nobeyama 45 m radio telescope. We have detected C$^{13}$CH with a signal-to-noise (S/N) ratio of 4, whereas no line of $^{13}$CCH was detected in either the dark clouds. The column densities of the normal species were derived to be ($1.66 \pm 0.18$)$\times 10^{14}$ cm$^{-2}$ and ($7.3 \pm 0.9$)$\times 10^{13}$ cm$^{-2}$ ($1 σ$) in L1521B and L134N, respectively. The column density ratios of $N$(C$^{13}$CH)/$N$($^{13}$CCH) were calculated to be $>1.1$ and $>1.4$ in L1521B and L134N, respectively. The characteristic that $^{13}$CCH is less abundant than C$^{13}$CH is likely common for dark clouds. Moreover, we find that the $^{12}$C/$^{13}$C ratios of CCH are much higher than those of HC$_{3}$N in L1521B by more than a factor of 2, as well as in Taurus Molecular Cloud-1 (TMC-1). In L134N, the differences in the $^{12}$C/$^{13}$C ratios between CCH and HC$_{3}$N seem to be smaller than those in L1521B and TMC-1. We discuss the origins of the $^{13}$C isotopic fractionation of CCH and investigate possible routes that cause the significantly high $^{12}$C/$^{13}$C ratio of CCH especially in young dark clouds, with the help of chemical simulations. The high $^{12}$C/$^{13}$C ratios of CCH seem to be caused by reactions between hydrocarbons (e.g., CCH, C$_{2}$H$_{2}$, $l,c$-C$_{3}$H) and C$^{+}$.

astro-ph.GA↗

arXiv2019

ALMA Detection of Vibrationally Excited ($v\mathrm{_t} = 1,2$) Acetic Acid toward NGC 6334I

Vibrationally excited states of detected interstellar molecules have been shown to account for a large portion of unidentified spectral lines in observed interstellar spectra toward chemically rich sources. Here, we present the first interstellar detection of the first and second vibrationally excited torsional states of acetic acid ($v_\mathrm{t} = 1, 2$) toward the high-mass star-forming region NGC 6334I. The observations presented were taken with the Atacama Large Millimeter/submillimeter Array in bands 4, 6, and 7 covering a frequency range of 130 - 352 GHz. By comparing a single excitation temperature model to the observations, the best-fit excitation temperature and column density are obtained to be 142(25) K and $1.12(7) \times 10^{17} \mathrm{cm^{-2}}$ respectively. Based on the intensity maps of the vibrationally excited CH$_3$COOH transitions, we found that the CH$_3$COOH emissions are compact and concentrated toward the MM1 and MM2 regions with a source size smaller than 2 arcsec. After locating the emission from different CH$_3$COOH transitions, which cover a large range of excitation energies, we are able to explain the variation of the CH$_3$COOH emission peak within the MM2 core by invoking continuum absorption or outflows.

astro-ph.GA↗

arXiv2019

Cyanopolyyne Chemistry around Massive Young Stellar Objects

Recent radio astronomical observations have revealed that HC$_{5}$N, the second shortest cyanopolyyne (HC$_{2n+1}$N), is abundant around some massive young stellar objects (MYSOs), which is not predicted by classical carbon-chain chemistry. For example, the observed HC$_{5}$N abundance toward the G28.28$-$0.36 MYSO is higher than that in L1527, which is one of the warm carbon chain chemistry (WCCC) sources, by more than one order of magnitude (Taniguchi et al., 2017). In this paper, we present chemical simulations of hot-core models with a warm-up period using the astrochemical code Nautilus. We find that the cyanopolyynes are formed initially in the gas phase and accreted onto the bulk and surface of granular ice mantles during the lukewarm phase, which occurs at $25 < T < 100$ K. In slow warm-up period models, the peak abundances occur as the cyanopolyynes desorb from dust grains after the temperature rises above 100 K. The lower limits of the abundances of HC$_{5}$N, CH$_{3}$CCH, and CH$_{3}$OH observed in the G28.28$-$0.36 MYSO can be reproduced in our hot-core models, after their desorption from dust grains. Moreover, previous observations suggested chemical diversity in envelopes around different MYSOs. We discuss possible interpretations of relationships between stages of the star-formation process and such chemical diversity, such as the different warm-up timescales. This timescale depends not only on the mass of central stars but also on the relationship between the size of warm regions and their infall velocity.

astro-ph.GA↗

arXiv2019

Modeling C-Shock Chemistry in Isolated Molecular Outflows

Shocks are a crucial probe for understanding the ongoing chemistry within ices on interstellar dust grains where many complex organic molecules (COMs) are believed to be formed. However, previous work has been limited to the initial liberation into the gas phase through non-thermal desorption processes such as sputtering. Here, we present results from the adapted three-phase gas-grain chemical network code NAUTILUS, with the inclusion of additional high-temperature reactions, non-thermal desorption, collisional dust heating, and shock-physics parameters. This enhanced model is capable of reproducing many of the molecular distributions and abundance ratios seen in our prior observations of the prototypical shocked-outflow L1157. In addition, we find that, among others, NH$_2$CHO, HCOOCH$_3$, and CH$_3$CHO have significant post-shock chemistry formation routes that differ from those of many other COMs observed in shocks. Finally, a number of selected species and phenomena are studied here with respect to their usefulness as shock tracers in various astrophysical sources.

astro-ph.GA↗

arXiv2019

On Simulating the Proton-Irradiation of O$_2$ and H$_2$O Ices Using Astrochemical-type Models, with Implications for Bulk Reactivity

Many astrochemical models today explicitly consider the species that comprise the bulk of interstellar dust grain ice-mantles separately from those in the top few monolayers. Bombardment of these ices by ionizing radiation - whether in the form of cosmic rays, stellar winds, or radionuclide emission - represents an astrochemically viable means of driving a rich chemistry even in the bulk of the ice-mantle, now supported by a large body of work in laboratory astrophysics. In this study, using an existing rate equation-based astrochemical code modified to include a method of considering radiation chemistry recently developed by us, we attempted to simulate two such studies in which (a) pure O$_2$ ice at 5 K and, (b) pure H$_2$O ice at 16 K and 77 K, were bombarded by keV H$^+$ ions. Our aims are twofold: (1) to test the capability of our newly developed method to replicate the results of ice-irradiation experiments, and (2) to determine in such a well-constrained system how bulk chemistry is best handled using the same gas-grain codes that are used to model the interstellar medium (ISM). We find that our modified astrochemical model is able to reproduce both the abundance of O$_3$ in the 5 K pure O$_2$ ice, as well as both the abundance of H$_2$O$_2$ in the 16 K water ice and the previously noted decrease of hydrogen peroxide at higher temperatures. However, these results require the assumption that radicals and other reactive species produced via radiolysis react quickly and non-diffusively with neighbors in the ice.

astro-ph.GA↗

arXiv2018

ALMA Observations of the Spatial Distribution of three C$_2$H$_4$O$_2$ Isomers towards Sgr B2(N)

The C$_2$H$_4$O$_2$ isomers have been previously investigated primarily via disparate sets of observations involving single dish and array measurements. The only attempt at using a uniform set of observations was performed with the IRAM 30 m observation in 2013 (Belloche et al. 2013). In this study, we present an intensive and rigorous spectral and morphological analysis of the C$_2$H$_4$O$_2$ isomers towards Sgr B2(N) with interferometers, ALMA Band 3 observations. We propose a quantitative selection method, which automates the determination of the most uncontaminated transitions and allows us to report the discovery of previously undetected transitions of the three isomers. With the least contaminated transitions, the high spatial-resolution millimeter maps of the C$_2$H$_4$O$_2$ isomers reveal that HCOOCH$_3$ and CH$_2$OHCHO each display two different velocity components, while only one velocity component of CH$_3$COOH is resolved. Moreover, the distribution of HCOOCH$_3$ is extended and offset from the continuum emission, unlike CH$_2$OHCHO and CH$_3$COOH, for which the low-velocity component is found to be compact and concentrated toward the continuum emission peak of Sgr B2(N). The distinct morphologies of these C$_2$H$_4$O$_2$ isomeric species indicate that HCOOCH$_3$ have significant differences in chemical processes than CH$_2$OHCHO and CH$_3$COOH, which display similar spatial distributions.

astro-ph.GA↗

arXiv2018

Astrochemical Kinetic Grid Models of Groups of Observed Molecular Abundances: Taurus Molecular Cloud 1 (TMC-1)

The emission line spectra of cyanoacetylene and methanol reveal chemical and physical heterogeneity on very small (< 0.1 pc) scales toward the peak in cyanopolyyne emission in the Taurus Molecular Cloud, TMC-1 (CP). We generate grids of homogeneous chemical models using a three-phase rate equation approach to obtain all time-dependent abundances spanning the physical conditions determined from molecular tracers of compact and extended regions of emission along this line of sight. Each time-dependent abundance is characterized by one of four features: a maximum/minimum, a monotonic increase/decrease, oscillatory behavior, or inertness. We similarly classify the time-dependent agreement between modeled and observed abundances by calculating both the root-mean-square logarithm difference and root-mean-square deviation between the modeled and observed abundances at every point in our grid models for three groups of molecules: (i) a composite group of all species present in both the observations and our chemical network G, (ii) the cyanopolyynes C = {HC$_3$N, HC$_5$N, HC$_7$N, HC$_9$N}, and (iii) the oxygen-containing organic species methanol and acetaldehyde S = {CH$_3$OH, CH$_3$CHO}. We discuss how the Bayesian uncertainties in the observed abundances constrain solutions within the grids of chemical models. The calculated best fit times at each grid point for each group are tabulated to reveal the minimum solution space of the grid models and the effects the Bayesian uncertainties have on the grid model solutions. The results of this approach separate the effect different physical conditions and model-free parameters have on reproducing accurately the abundances of different groups of observed molecular species.

astro-ph.GA↗

arXiv2018

On Cosmic Ray-Driven Grain Chemistry in Cold Core Models

In this paper, we present preliminary results illustrating the effect of cosmic rays on solid-phase chemistry in models of both TMC-1 and several sources with physical conditions identical to TMC-1 except for hypothetically enhanced ionization rates. Using a recent theory for the addition of cosmic ray-induced reactions to astrochemical models, we calculated the radiochemical yields, called $G$ values, for the primary dust grain ice-mantle constituents. We show that the inclusion of this non-thermal chemistry can lead to the formation of complex organic molecules from simpler ice-mantle constituents, even under cold core conditions. In addition to enriching ice-mantles, we find that these new radiation-chemical processes can lead to increased gas-phase abundances as well, particularly for HOCO, NO$_2$, HC$_2$O, methyl formate (HCOOCH$_3$), and ethanol (CH$_3$CH$_2$OH). These model results imply that HOCO - and perhaps NO$_2$ - might be observable in TMC-1. Future detections of either of these two species in cold interstellar environments could provide strong support for the importance of cosmic ray-driven radiation chemistry. The increased gas-phase abundance of methyl formate can be compared with abundances achieved through other formation mechanisms such as pure gas-phase chemistry and three-body surface reactions.

astro-ph.GA↗

arXiv2018

Multiple paths of deuterium fractionation in protoplanetary disks

We investigate deuterium chemistry coupled with the nuclear spin-state chemistry of H$_2$ and H$_3^+$ in protoplanetary disks. Multiple paths of deuterium fractionation are found; exchange reactions with D atoms, such as HCO$^+$ + D, are effective in addition to those with HD. In a disk model with grain sizes appropriate for dark clouds, the freeze-out of molecules is severe in the outer midplane, while the disk surface is shielded from UV radiation. Gaseous molecules, including DCO$^+$, thus become abundant at the disk surface, which tends to make their column density distribution relatively flat. If the dust grains have grown to millimeter size, the freeze-out rate of neutral species is reduced, and the abundances of gaseous molecules, including DCO$^+$ and N$_2$D$^+$, are enhanced in the cold midplane. Turbulent diffusion transports D atoms and radicals at the disk surface to the midplane, and stable ice species in the midplane to the disk surface. The effects of turbulence on chemistry are thus multifold; while DCO$^+$ and N$_2$D$^+$ abundances increase or decrease depending on the regions, HCN and DCN in the gas and ice are much reduced at the innermost radii, compared with the model without turbulence. When cosmic rays penetrate the disk, the ortho-to-para ratio (OPR) of H$_2$ is found to be thermal in the disk, except in the cold ($\lesssim 10$ K) midplane. We also analyze the OPR of H$_3^+$ and H$_2$D$^+$, as well as the main reactions of H$_2$D$^+$, DCO$^+$, and N$_2$D$^+$ to analytically derive their abundances in the cold midplane.

astro-ph.SR↗