arXiv subjects

Eric Herbst

Publications and source records attributed to Eric Herbst.

At least 73 records · Page 4Linked to original sources

arXiv2018

High Spectral Resolution SOFIA/EXES Observations of C2H2 towards Orion-IRc2

We present high-spectral resolution observations from 12.96 - 13.33 microns towards Orion IRc2 using the mid-infrared spectrograph, EXES, on SOFIA. These observations probe the physical and chemical conditions of the Orion hot core, which is sampled by a bright, compact, mid-infrared background continuum source in the region, IRc2. All ten of the rovibrational C2H2 transitions expected in our spectral coverage, are detected with high S/N, yielding continuous coverage of the R-branch lines from J=9-8 to J=18-17, including both ortho and para species. Eight of these rovibrational transitions are newly reported detections. The isotopologue, 13CCH2, is clearly detected with high signal-to-noise. This enabled a direct measurement of the 12C/13C isotopic ratio for the Orion hot core of 14 +/- 1 and an estimated maximum value of 21. We also detected several HCN rovibrational lines. The ortho and para C2H2 ladders are clearly separate and tracing two different temperatures, 226 K and 164 K, respectively, with a non-equilibrium ortho to para ratio (OPR) of 1.7 +\- 0.1. Additionally, the ortho and para V_LSR values differ by about 1.8 +/- 0.2 km/s, while, the mean line widths differ by 0.7 +/- 0.2 km/s, suggesting that these species are not uniformly mixed along the line of sight to IRc2. We propose that the abnormally low C2H2 OPR could be a remnant from an earlier, colder phase, before the density enhancement (now the hot core) was impacted by shocks generated from an explosive event 500 yrs ago.

astro-ph.GA↗

arXiv2018

Detection of the Aromatic Molecule Benzonitrile ($c$-C$_6$H$_5$CN) in the Interstellar Medium

Polycyclic aromatic hydrocarbons and polycyclic aromatic nitrogen heterocycles are thought to be widespread throughout the Universe, because these classes of molecules are probably responsible for the unidentified infrared bands, a set of emission features seen in numerous Galactic and extragalactic sources. Despite their expected ubiquity, astronomical identification of specific aromatic molecules has proven elusive. We present the discovery of benzonitrile ($c$-C$_6$H$_5$CN), one of the simplest nitrogen-bearing aromatic molecules, in the interstellar medium. We observed hyperfine-resolved transitions of benzonitrile in emission from the molecular cloud TMC-1. Simple aromatic molecules such as benzonitrile may be precursors for polycyclic aromatic hydrocarbon formation, providing a chemical link to the carriers of the unidentified infrared bands.

astro-ph.GA↗

arXiv2017

A Molecular Line Survey toward the Nearby Galaxies NGC 1068, NGC 253, and IC 342 at 3 mm with the Nobeyama 45-m Radio Telescope: Impact of an AGN on 1 kpc Scale Molecular Abundances

It is important to investigate the relationships between the power sources and the chemical compositions of galaxies for understanding the scenario of galaxy evolution. We carried out an unbiased molecular line survey towards AGN host galaxy NGC1068, and prototypical starburst galaxies, NGC 253 and IC 342, with the Nobeyama 45-m telescope in the 3-mm band. The advantage of this line survey is that the obtained spectra have the highest angular resolution ever obtained with single-dish telescopes. In particular, the beam size of this telescope is ~15"--19", which is able to spatially separate the nuclear molecular emission from that of the starburst ring (d~30") in NGC 1068. We successfully detected approximately 23 molecular species in each galaxy, and calculated rotation temperatures and column densities. We estimate the molecular fractional abundances with respect to 13CO and CS molecules and compare them among three galaxies in order to investigate the chemical signatures of an AGN environment. As a result, we found clear trends on the abundances of molecules surrounding the AGN on 1 kpc scale. HCN, H13CN, CN, 13CN, and HC3N are more abundant, and CH3CCH is deficient in NGC 1068 compared with the starburst galaxies. High abundances of HCN, H13CN, and HC3N suggest that the circumnuclear disk in NGC 1068 is in a high-temperature environment. The reason for the non-detection of CH3CCH is likely to be dissociation by high energy radiation or less sublimation of a precursor of CH3CCH from grains.

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

Detection of HC$_5$N and HC$_7$N Isotopologues in TMC-1 with the Green Bank Telescope

We report the first interstellar detection of DC$_7$N and six $^{13}$C-bearing isotopologues of HC$_7$N toward the dark cloud TMC-1 through observations with the Green Bank Telescope, and confirm the recent detection of HC$_5$$^{15}$N. For the average of the $^{13}$C isotopomers, DC$_7$N, and HC$_5$$^{15}$N, we derive column densities of 1.9(2)$\times$10$^{11}$, 2.5(9)$\times$10$^{11}$, and 1.5(4)$\times$10$^{11}$ cm$^{-2}$, respectively. The resulting isotopic ratios are consistent with previous values derived from similar species in the source, and we discuss the implications for the formation chemistry of the observed cyanopolyynes. Within our uncertainties, no significant $^{13}$C isotopomer variation is found for HC$_7$N, limiting the significance CN could have in its production. The results further show that, for all observed isotopes, HC$_5$N may be isotopically depleted relative to HC$_3$N and HC$_7$N, suggesting that reactions starting from smaller cyanopolyynes may not be efficient to form HC$_{n}$N. This leads to the conclusion that the dominant production route may be the reaction between hydrocarbon ions and nitrogen atoms.

astro-ph.GA↗

arXiv2017

The ortho-to-para ratio of H$_2$Cl$^+$: Quasi-classical trajectory calculations and new simulations in light of new observations

Multi-hydrogenated species with proper symmetry properties can present different spin configurations, and thus exist under different spin symmetry forms, labeled as para and ortho for two-hydrogen molecules. We investigated here the ortho-to-para ratio (OPR) of H$_2$Cl$^+$ in the light of new observations performed in the z=0.89 absorber toward the lensed quasar PKS 1830-211 with the Atacama Large Millimeter/submillimeter Array (ALMA). Two independent lines of sight were observed, to the southwest (SW) and northeast (NE) images of the quasar, with OPR values found to be $3.15 \pm 0.13$ and $3.1 \pm 0.5$ in each region, respectively, in agreement with a spin statistical weight of 3:1. An OPR of 3:1 for a molecule containing two identical hydrogen nuclei can refer to either a statistical result or a high-temperature limit depending on the reaction mechanism leading to its formation. It is thus crucial to identify rigorously how OPRs are produced in order to constrain the information that these probes can provide. To understand the production of the H$_2$Cl$^+$ OPR, we undertook a careful theoretical study of the reaction mechanisms involved with the aid of quasi-classical trajectory calculations on a new global potential energy surface fit to a large number of high-level ab initio data. Our study shows that the major formation reaction for H$_2$Cl$^+$ produces this ion via a hydrogen abstraction rather than a scrambling mechanism. Such a mechanism leads to a 3:1 OPR, which is not changed by destruction and possible thermalization reactions for H$_2$Cl$^+$ and is thus likely to be the cause of observed 3:1 OPR ratios, contrary to the normal assumption of scrambling.

astro-ph.GA↗

arXiv2017

The Molecular Chemistry of Diffuse and Translucent Clouds in the Line-of-Sight to Sgr B2

The 1-50 GHz GBT PRIMOS data contains ~50 molecular absorption lines observed in diffuse and translucent clouds located in the Galactic Center, Bar, and spiral arms in the line-of-sight to Sgr B2(N). We measure the column densities and estimate abundances, relative to H2, of 11 molecules and additional isotopologues. We use absorption by optically thin transitions of c-C3H2 to estimate the N(H2), and argue that this method is preferable to more commonly used methods. We discuss the kinematic structure and abundance patterns of small molecules including the sulfur-bearing species CS, SO, CCS, H2CS, and HCS+; oxygen-bearing molecules OH, SiO, and H2CO; and simple hydrocarbon molecules c-C3H2, l-C3H, and l-C3H+. We discuss the implications of the observed chemistry for the structure of the gas and dust in the ISM. Highlighted results include the following. First, whereas gas in the disk has a molecular hydrogen fraction of 0.65, clouds on the outer edge of the Galactic Bar and in or near the Galactic Center have molecular fractions of 0.85 and >0.9, respectively. Second, we observe trends in isotope ratios with Galactocentric distance; while carbon and silicon show enhancement of the rare isotopes at low Galactocentric distances, sulfur exhibits no trend with Galactocentric distance; the ratio of c-C3H2/c-H13CCCH provides a good estimate of the 12C:13C ratio, whereas H2CO/H2^13CO exhibits fractionation. Third, we report the presence of l-C3H+ in diffuse clouds for the first time. Finally, we suggest that CS has an enhanced abundance within higher density clumps of material in the disk, and therefore may be diagnostic of cloud conditions. If this holds, the diffuse clouds in the Galactic disk contain multiple embedded hyperdensities in a clumpy structure, and the density profile is not a simple function of A_V.

astro-ph.GA↗

arXiv2017

A new study of the chemical structure of the Horsehead nebula: the influence of grain-surface chemistry

A wide variety of molecules have recently been detected in the Horsehead nebula photodissociation region (PDR) suggesting that: (i) gas-phase and grain chemistries should both contribute to the formation of organic molecules, and (ii) far-ultraviolet (FUV) photodesorption may explain the release into the gas phase of grain surface species. In order to tackle these specific problems and more generally in order to better constrain the chemical structure of these types of environments we present a study of the Horsehead nebula gas-grain chemistry. To do so we used the 1D astrochemical gas-grain code Nautilus with an appropriate physical structure computed with the Meudon PDR Code and compared our modeled outcomes with published observations and with previously modeled results when available. The use of a large set of chemical reactions coupled with the time-dependent code Nautilus allows us to reproduce most of the observations well, including those of the first detections in a PDR of the organic molecules HCOOH, CH2CO, CH3CHO and CH3CCH, which are mostly associated with hot cores. We also provide some abundance predictions for other molecules of interest. Understanding the chemistry behind the detection of these organic molecules is crucial to better constrain the environments these molecules can probe.

astro-ph.GA↗

arXiv2017

Detection of Interstellar HC$_5$O in TMC-1 with the Green Bank Telescope

We report the detection of the carbon-chain radical HC$_5$O for the first time in the interstellar medium toward the dark cloud TMC-1 using the 100 m Green Bank Telescope. We observe four hyperfine components of this radical in the $J = 17/2 \rightarrow 15/2$ rotational transition that originates from the $^2Π_{1/2}$ fine structure level of its ground state, and calculate an abundance of $n/n_{H_2}$ = $1.7\times 10^{-10}$, assuming an excitation temperature of $T_{ex} = 7$~K. No indication of HC$_3$O, HC$_4$O, HC$_6$O, is found in these or archival observations of the source, while we report tentative evidence for HC$_7$O. We compare calculated upper limits, and the abundance of HC$_5$O to predictions based on (1) the abundance trend of the analogous HC$_n$N family in TMC-1 and (2) a gas-grain chemical model. We find that the gas-grain chemical model well reproduces the observed abundance of HC$_5$O, as well as the upper limits of HC$_3$O, HC$_6$O, and HC$_7$O, but HC$_4$O is over produced. The prospects for astronomical detection of both shorter and longer HC$_n$O chains are discussed.

astro-ph.GA↗

arXiv2017

A new model of the chemistry of ionizing radiation in solids: CIRIS

The collisions between high-energy ions and solids can result in significant physical and chemical changes to the material. These effects are potentially important for better understanding the chemistry of interstellar and planetary bodies, which are exposed to cosmic radiation and the solar wind, respectively, however, modeling such collisions on a detailed microscopic basis has thus far been largely unsuccessful. To that end, a new model, entitled CIRIS: the Chemistry of Ionizing Radiation in Solids, was created to calculate the physical and chemical effects of the irradiation of solid materials. With the new code, we simulate O2 ice irradiated with 100 keV protons. Our models are able to reproduce the measured ozone abundances of a previous experimental study, as well as independently predict the approximate thickness of the ice used in that work.

physics.chem-ph↗

arXiv2017

The Possibility of Forming Propargyl Alcohol in the Interstellar Medium

Propargyl alcohol (HC2CH2OH, PA) has yet to be observed in the interstellar medium (ISM) although one of its stable isomers, propenal (CH2CHCHO), has already been detected in Sagittarius B2(N) with the 100-meter Green Bank Telescope in the frequency range $18-26$ GHz. In this paper, we investigate the formation of propargyl alcohol along with one of its deuterated isotopomers, HC2CH2OD(OD-PA), in a dense molecular cloud. Various pathways for the formation of PA in the gas and on ice mantles surrounding dust particles are discussed. We use a large gas-grain chemical network to study the chemical evolution of PA and its deuterated isotopomer. Our results suggest that gaseous HC2CH2OH can most likely be detected in hot cores or in collections of hot cores such as the star-forming region Sgr B2(N). A simple LTE (Local thermodynamic equilibrium) radiative transfer model is employed to check the possibility of detecting PA and OD-PA in the millimeter-wave regime. In addition, we have carried out quantum chemical calculations to compute the vibrational transition frequencies and intensities of these species in the infrared for perhaps future use in studies with the James Webb Space Telescope (JWST).

astro-ph.GA↗

arXiv2016

Theory of Gas Phase Scattering and Reactivity for Astrochemistry

Because of the very peculiar conditions of chemistry in many astrophysical gases (low densities, mostly low temperatures, kinetics-dominated chemical evolution), great efforts have been devoted to study molecular signatures and chemical evolution. While experiments are being performed in many laboratories, it appears that the efforts directed towards theoretical works are not as strong. This report deals with the present status of chemical physics/physical chemistry theory, for the qualitative and quantitative understanding of kinetics of molecular scattering, being it reactive or inelastic. By gathering several types of expertise, from applied mathematics to physical chemistry, dialog is made possible, as a step towards new and more adapted theoretical frameworks, capable of meeting the theoretical, methodological and numerical challenges of kinetics-dominated gas phase chemistry in astrophysical environments. A state of the art panorama is presented, alongside present-day strengths and shortcomings. However, coverage is not complete, being limited in this report to actual attendance of the workshop. Some paths towards relevant progress are proposed.

astro-ph.IM↗

arXiv2016

On the Inference of the Cosmic Ray Ionization Rate $ζ$ from the HCO$^+$-to-DCO$^+$ Abundance Ratio: The Effect of Nuclear Spin

The chemistry of dense interstellar regions was analyzed using a time-dependent gas-grain astrochemical simulation and a new chemical network that incorporates deuterated chemistry taking into account nuclear spin-states for the hydrogen chemistry and its deuterated isotopologues. With this new network, the utility of the [HCO$^+$]/[DCO$^+$] abundance ratio as a probe of the cosmic ray ionization rate has been reexamined, with special attention paid to the effect of the initial value of the molecular hydrogen ortho-to-para ratio (OPR). After discussing the use of the probe for cold cores, we then compare our results with previous theoretical and observational results for a molecular cloud close to the supernova remnant W51C, which is thought to have an enhanced cosmic ray ionization rate $ζ$ caused by the nearby $γ$-ray source. In addition, we attempt to use our approach to estimate the cosmic ray ionization rate for L1174, a dense core with an embedded star. Beyond the previously known sensitivity of [HCO$^+$]/[DCO$^+$] to $ζ$, we demonstrate its additional dependence on the initial OPR and, secondarily, on the age of the source, its temperature, and its density. We conclude that the usefulness of the [HCO$^+$]/[DCO$^+$] abundance ratio to constrain the cosmic ray ionization rate in dense regions increases with source age and ionization rate as the ratio becomes far less sensitive to the initial value of the OPR.

astro-ph.GA↗

arXiv2016

The ortho-to-para ratio of interstellar NH$_2$: Quasi-classical trajectory calculations and new simulations

Based on recent $Herschel$ results, the ortho-to-para ratio (OPR) of NH$_2$ has been measured towards the following high-mass star-forming regions: W31C (G10.6-0.4), W49N (G43.2-0.1), W51 (G49.5-0.4), and G34.3+0.1. The OPR at thermal equilibrium ranges from the statistical limit of three at high temperatures to infinity as the temperature tends toward zero, unlike the case of H$_{2}$. Depending on the position observed along the lines-of-sight, the OPR was found to lie either slightly below the high temperature limit of three (in the range $2.2-2.9$) or above this limit ($\sim3.5$, $\gtrsim 4.2$, and $\gtrsim 5.0$). In low temperature interstellar gas, where the H$_{2}$ is para-enriched, our nearly pure gas-phase astrochemical models with nuclear-spin chemistry can account for anomalously low observed NH$_2$-OPR values. We have tentatively explained OPR values larger than three by assuming that spin thermalization of NH$_2$ can proceed at least partially by H-atom exchange collisions with atomic hydrogen, thus increasing the OPR with decreasing temperature. In this paper, we present quasi-classical trajectory calculations of the H-exchange reaction NH$_2$ + H, which show the reaction to proceed without a barrier, confirming that the H-exchange will be efficient in the temperature range of interest. With the inclusion of this process, our models suggest both that OPR values below three arise in regions with temperatures $\gtrsim20-25$~K, depending on time, and values above three but lower than the thermal limit arise at still lower temperatures.

astro-ph.GA↗

arXiv2016

First detection of gas-phase methanol in a protoplanetary disk

The first detection of gas-phase methanol in a protoplanetary disk (TW Hya) is presented. In addition to being one of the largest molecules detected in disks to date, methanol is also the first disk organic molecule with an unambiguous ice chemistry origin. The stacked methanol emission, as observed with ALMA, is spectrally resolved and detected across six velocity channels ($>3 σ$), reaching a peak signal-to-noise of $5.5σ$, with the kinematic pattern expected for TW~Hya. Using an appropriate disk model, a fractional abundance of $3\times 10^{-12} - 4 \times 10^{-11}$ (with respect to H$_2$) reproduces the stacked line profile and channel maps, with the favoured abundance dependent upon the assumed vertical location (midplane versus molecular layer). The peak emission is offset from the source position suggesting that the methanol emission has a ring-like morphology: the analysis here suggests it peaks at $\approx 30$~AU reaching a column density $\approx 3-6\times10^{12}$~cm$^{-2}$. In the case of TW Hya, the larger (up to mm-sized) grains, residing in the inner 50~AU, may thus host the bulk of the disk ice reservoir. The successful detection of cold gas-phase methanol in a protoplanetary disk implies that the products of ice chemistry can be explored in disks, opening a window to studying complex organic chemistry during planetary system formation.

astro-ph.EP↗

arXiv2016

CSO and CARMA Observations of L1157. II. Chemical Complexity in the Shocked Outflow

L1157, a molecular dark cloud with an embedded Class 0 protostar possessing a bipolar outflow, is an excellent source for studying shock chemistry, including grain-surface chemistry prior to shocks, and post-shock, gas-phase processing. The L1157-B1 and B2 positions experienced shocks at an estimated ~2000 and 4000 years ago, respectively. Prior to these shock events, temperatures were too low for most complex organic molecules to undergo thermal desorption. Thus, the shocks should have liberated these molecules from the ice grain-surfaces en masse, evidenced by prior observations of SiO and multiple grain mantle species commonly associated with shocks. Grain species, such as OCS, CH3OH, and HNCO, all peak at different positions relative to species that are preferably formed in higher velocity shocks or repeatedly-shocked material, such as SiO and HCN. Here, we present high spatial resolution (~3") maps of CH3OH, HNCO, HCN, and HCO+ in the southern portion of the outflow containing B1 and B2, as observed with CARMA. The HNCO maps are the first interferometric observations of this species in L1157. The maps show distinct differences in the chemistry within the various shocked regions in L1157B. This is further supported through constraints of the molecular abundances using the non-LTE code RADEX (Van der Tak et al. 2007). We find the east/west chemical differentiation in C2 may be explained by the contrast of the shock's interaction with either cold, pristine material or warm, previously-shocked gas, as seen in enhanced HCN abundances. In addition, the enhancement of the HNCO abundance toward the the older shock, B2, suggests the importance of high-temperature O-chemistry in shocked regions.

astro-ph.GA↗

arXiv2016

Unified Microscopic-Macroscopic Monte Carlo Simulations of Complex Organic Molecule Chemistry in Cold Cores

The recent discovery of methyl formate and dimethyl ether in the gas phase of cold cores with temperatures as cold as 10 K challenges our previous astrochemical models concerning the formation of complex organic molecules. The strong correlation between the abundances and distributions of methyl formate and dimethyl ether further shows that current astrochemical models may be missing important chemical processes in cold astronomical sources. We investigate a scenario in which complex organic molecules and the methoxy radical can be formed on dust grains via a so-called "chain reaction" mechanism, in a similar manner to CO$_2$. A unified gas-grain microscopic-macroscopic Monte Carlo approach with both normal and interstitial sites for icy grain mantles is used to perform the chemical simulations. Reactive desorption with varying degrees of efficiency is included to enhance the non-thermal desorption of species formed on cold dust grains. In addition, varying degrees of efficiency for the surface formation of methoxy are also included. The observed abundances of a variety of organic molecules in cold cores can be reproduced in our models. The strong correlation between the abundances of methyl formate and dimethyl ether in cold cores can also be explained. Non-diffusive chemical reactions on dust grain surfaces may play a key role in the formation of some complex organic molecules.

astro-ph.SR↗

arXiv2015

Water deuteration and ortho-to-para nuclear spin ratio of H2 in molecular clouds formed via the accumulation of HI gas

We investigate the water deuteration ratio and ortho-to-para nuclear spin ratio of H2 (OPR(H2)) during the formation and early evolution of a molecular cloud, following the scenario that accretion flows sweep and accumulate HI gas to form molecular clouds. We follow the physical evolution of post-shock materials using a one-dimensional shock model, with post-processing gas-ice chemistry simulations. This approach allows us to study the evolution of the OPR(H2) and water deuteration ratio without an arbitrary assumption concerning the initial molecular abundances, including the initial OPR(H2). When the conversion of hydrogen into H2 is almost complete, the OPR(H2) is already much smaller than the statistical value of three due to the spin conversion in the gas phase. As the gas accumulates, the OPR(H2) decreases in a non-equilibrium manner. We find that water ice can be deuterium-poor at the end of its main formation stage in the cloud, compared to water vapor observed in the vicinity of low-mass protostars where water ice is likely sublimated. If this is the case, the enrichment of deuterium in water should mostly occur at somewhat later evolutionary stages of star formation, i.e., cold prestellar/protostellar cores. The main mechanism to suppress water ice deuteration in the cloud is the cycle of photodissociation and reformation of water ice, which efficiently removes deuterium from water ice chemistry. The removal efficiency depends on the main formation pathway of water ice. The OPR(H2) plays a minor role in water ice deuteration at the main formation stage of water ice.

astro-ph.GA↗