arXiv subjects

Robin T. Garrod

Publications and source records attributed to Robin T. Garrod.

52 records · Page 3Linked to original sources

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↗

arXiv2016

Laboratory spectroscopic study and astronomical detection of vibrationally excited n-propyl cyanide

We performed a spectral line survey called Exploring Molecular Complexity with ALMA (EMoCA) toward Sagittarius~B2(N) between 84.1 and 114.4 GHz with the Atacama Large Millimeter/submillimeter Array (ALMA) in its Cycles 0 and 1. We determined line intensities of n-propyl cyanide in the ground vibrational states of its gauche and anti conformers toward the hot molecular core Sagittarius B2(N2) which suggest that we should also be able to detect transitions pertaining to excited vibrational states. We wanted to determine spectroscopic parameters of low-lying vibrational states of both conformers of n-propyl cyanide to search for them in our ALMA data. We recorded laboratory rotational spectra of n-propyl cyanide in two spectral windows between 36 and 127 GHz. We searched for emission lines produced by these states in the ALMA spectrum of Sagittarius B2(N2). We modeled their emission and the emission of the ground vibrational states assuming local thermodynamic equilibrium (LTE). We have made extensive assignments of a- and b-type transitions of the four lowest vibrational states of the gauche conformer which reach J and Ka quantum numbers of 65 and 20, respectively. We assigned mostly a-type transitions for the anti conformer with J and Ka quantum numbers up to 48 and 24, respectively. Rotational and Fermi perturbations between two anti states allowed us to determine their energy difference. The resulting spectroscopic parameters enabled us to identify transitions of all four vibrational states of each conformer in our ALMA data. The emission features of all states, including the ground vibrational state, are well-reproduced with the same LTE modeling parameters, which gives us confidence in the reliability of the identifications, even for the states with only one clearly detected line.

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arXiv2015

The Effects of Grain Size and Temperature Distributions on the Formation of Interstellar Ice Mantles

Computational models of interstellar gas-grain chemistry have historically adopted a single dust-grain size of 0.1 micron, assumed to be representative of the size distribution present in the interstellar medium. Here, we investigate the effects of a broad grain-size distribution on the chemistry on dust-grain surfaces and the subsequent build-up of molecular ices on the grains, using a three-phase gas-grain chemical model of a quiescent dark cloud. We include an explicit treatment of the grain temperatures, governed both by the visual extinction of the cloud and the size of each individual grain-size population. We find that the temperature difference plays a significant role in determining the total bulk ice composition across the grain-size distribution, while the effects of geometrical differences between size populations appear marginal. We also consider collapse from a diffuse to a dark cloud, allowing dust temperatures to fall. Under the initial diffuse conditions, small grains are too warm to promote grain-mantle build-up, with most ices forming on the mid-sized grains. As collapse proceeds, the more abundant, smallest grains cool and become the dominant ice carriers; the large population of small grains means that this ice is distributed across many grains, with perhaps no more than 40 monolayers of ice each (versus several hundred assuming a single grain size). This effect may be important for the subsequent processing and desorption of the ice during the hot-core phase of star-formation, exposing a significant proportion of the ice to the gas phase, increasing the importance of ice-surface chemistry and surface-gas interactions.

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arXiv2015

Formation of hydroxylamine on dust grains via ammonia oxidation

The quest to detect prebiotic molecules in space, notably amino acids, requires an understanding of the chemistry involving nitrogen atoms. Hydroxylamine (NH$_2$OH) is considered a precursor to the amino acid glycine. Although not yet detected, NH$_2$OH is considered a likely target of detection with ALMA. We report on an experimental investigation of the formation of hydroxylamine on an amorphous silicate surface via the oxidation of ammonia. The experimental data are then fed into a simulation of the formation of NH$_2$OH in dense cloud conditions. On ices at 14 K and with a modest activation energy barrier, NH$_2$OH is found to be formed with an abundance that never falls below a factor 10 with respect to NH$_3$. Suggestions of conditions for future observations are provided.

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arXiv2015

Complex organic molecules in organic-poor massive young stellar objects

Massive young stellar objects (MYSOs) with hot cores are classic sources of complex organic molecules. The origins of these molecules in such sources, as well as the small- and large-scale differentiation between nitrogen- and oxygen-bearing complex species, are poorly understood. We aim to use complex molecule abundances toward a chemically less explored class of MYSOs with weak hot organic emission lines to constrain the impact of hot molecular cores and initial ice conditions on the chemical composition toward MYSOs. We use the IRAM 30m and the Submillimeter Array to search for complex organic molecules over 8-16 GHz in the 1~mm atmospheric window toward three MYSOs with known ice abundances, but without luminous molecular hot cores. Complex molecules are detected toward all three sources at comparable abundances with respect to CH$_3$OH to classical hot core sources. The relative importance of CH$_3$CHO, CH$_3$CCH, CH$_3$OCH$_3$, CH$_3$CN, and HNCO differ between the organic-poor MYSOs and hot cores, however. Furthermore, the N-bearing molecules are generally concentrated toward the source centers, while most O- and C-bearing molecules are present both in the center and in the colder envelope. Gas-phase HNCO/CH$_3$OH ratios are tentatively correlated with the ratios of NH$_3$ ice over CH$_3$OH ice in the same lines of sight, which is consistent with new gas-grain model predictions. Hot cores are not required to form complex organic molecules, and source temperature and initial ice composition both seem to affect complex organic distributions toward MYSOs. To quantify the relative impact of temperature and initial conditions requires, however, a larger spatially resolved survey of MYSOs with ice detections.

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arXiv2014

Detection of a branched alkyl molecule in the interstellar medium: iso-propyl cyanide

The largest non-cyclic molecules detected in the interstellar medium (ISM) are organic with a straight-chain carbon backbone. We report an interstellar detection of a branched alkyl molecule, iso-propyl cyanide (i-C3H7CN), with an abundance 0.4 times that of its straight-chain structural isomer. This detection suggests that branched carbon-chain molecules may be generally abundant in the ISM. Our astrochemical model indicates that both isomers are produced within or upon dust grain ice mantles through the addition of molecular radicals, albeit via differing reaction pathways. The production of iso-propyl cyanide appears to require the addition of a functional group to a non-terminal carbon in the chain. Its detection therefore bodes well for the presence in the ISM of amino acids, for which such side-chain structure is a key characteristic.

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arXiv2013

Three-dimensional off-lattice Monte Carlo kinetics simulations of interstellar grain chemistry and ice structure

The first off-lattice Monte Carlo kinetics model of interstellar dust-grain surface chemistry is presented. The positions of all surface particles are determined explicitly, according to the local potential minima resulting from the pair-wise interactions of contiguous atoms and molecules, rather than by a pre-defined lattice structure. The model is capable of simulating chemical kinetics on any arbitrary dust-grain morphology, as determined by the user-defined positions of each individual dust-grain atom. A simple method is devised for the determination of the most likely diffusion pathways and their associated energy barriers for surface species. The model is applied to a small, idealized dust grain, adopting various gas densities and using a small chemical network. Hydrogen and oxygen atoms accrete onto the grain, to produce H2O, H2, O2 and H2O2. The off-lattice method allows the ice structure to evolve freely; ice mantle porosity is found to be dependent on the gas density, which controls the accretion rate. A gas density of 2 x 10^{4} cm^{-3}, appropriate to dark interstellar clouds, is found to produce a fairly smooth and non-porous ice mantle. At all densities, H2 molecules formed on the grains collect within the crevices that divide nodules of ice, and within micropores (whose extreme inward curvature produces strong local potential minima). The larger pores produced in the high-density models are not typically filled with H2. Direct deposition of water molecules onto the grain indicates that amorphous ices formed in this way may be significantly more porous than interstellar ices that are formed by surface chemistry.

astro-ph.IM↗

arXiv2013

The Spatial Distribution of Organics toward the High-Mass YSO NGC 7538 IRS9

Based on astrochemical theory, the complex molecular composition around high-mass YSOs should evolve from the outer envelope in toward the central hot region as a sequence of temperature dependent chemical pathways are activated in ices and in the gas-phase. The resulting complex molecules have been broadly classified into three generations dependent on the temperature (<25, >25, and >100 K) required for formation. We combine IRAM 30m and Submillimeter Array observations to explore the spatial distribution of organic molecules around the high-mass young stellar object NGC 7538 IRS9, whose weak complex molecule emission previously escaped detection, quantifying the emission and abundance profiles of key organic molecules as a function of distance from the central protostar. We find that emission from N-bearing organics and saturated O-bearing organics present large increases in emission around 8000 AU and R<3000 AU, while O-bearing molecules and hydrocarbons do not. The increase in flux from some complex molecules in the envelope, around 8000 AU or 25 K, is consistent with recent model predictions of an onset of complex ice chemistry at 20-30 K. The emission increase for some molecules at R<3000 AU suggests the presence of a weak hot core, where thermal ice evaporation and hot gas-phase chemistry drives the chemistry. Complex organics thus form at all radii and temperatures around this protostar, but the composition changes dramatically as the temperature increases, which is used to constrain the chemical generation(s) to which different classes of molecule belong.

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arXiv2013

A three-phase chemical model of hot cores: the formation of glycine

A new chemical model is presented that simulates fully-coupled gas-phase, grain-surface and bulk-ice chemistry in hot cores. Glycine (NH2CH2COOH), the simplest amino acid, and related molecules such as glycinal, propionic acid and propanal, are included in the chemical network. Glycine is found to form in moderate abundance within and upon dust-grain ices via three radical-addition mechanisms, with no single mechanism strongly dominant. Glycine production in the ice occurs over temperatures ~40-120 K. Peak gas-phase glycine fractional abundances lie in the range 8 x 10^{-11} - 8 x 10^{-9}, occuring at ~200 K, the evaporation temperature of glycine. A gas-phase mechanism for glycine production is tested and found insignificant, even under optimal conditions. A new spectroscopic radiative-transfer model is used, allowing the translation and comparison of the chemical-model results with observations of specific sources. Comparison with the nearby hot-core source NGC 6334 IRS1 shows excellent agreement with integrated line intensities of observed species, including methyl formate. The results for glycine are consistent with the current lack of a detection of this molecule toward other sources; the high evaporation temperature of glycine renders the emission region extremely compact. Glycine detection with ALMA is predicted to be highly plausible, for bright, nearby sources with narrow emission lines. Photodissociation of water and subsequent hydrogen-abstraction from organic molecules by OH, and NH2, are crucial to the build-up of complex organic species in the ice. The inclusion of alternative branches within the network of radical-addition reactions appears important to the abundances of hot-core molecules; less favorable branching ratios may remedy the anomalously high abundance of glycolaldehyde predicted by this and previous models.

astro-ph.GA↗

arXiv2012

From Prestellar to Protostellar Cores II. Time Dependence and Deuterium Fractionation

We investigate the molecular evolution and D/H abundance ratios that develop as star formation proceeds from a dense-cloud core to a protostellar core, by solving a gas-grain reaction network applied to a 1-D radiative hydrodynamic model with infalling fluid parcels. Spatial distributions of gas and ice-mantle species are calculated at the first-core stage, and at times after the birth of a protostar. Gas-phase methanol and methane are more abundant than CO at radii $r\lesssim 100$ AU in the first-core stage, but gradually decrease with time, while abundances of larger organic species increase. The warm-up phase, when complex organic molecules are efficiently formed, is longer-lived for those fluid parcels in-falling at later stages. The formation of unsaturated carbon chains (warm carbon-chain chemistry) is also more effective in later stages; C$^+$, which reacts with CH$_4$ to form carbon chains, increases in abundance as the envelope density decreases. The large organic molecules and carbon chains are strongly deuterated, mainly due to high D/H ratios in the parent molecules, determined in the cold phase. We also extend our model to simulate simply the chemistry in circumstellar disks, by suspending the 1-D infall of a fluid parcel at constant disk radii. The species CH$_3$OCH$_3$ and HCOOCH$_3$ increase in abundance in $10^4-10^5$ yr at the fixed warm temperature; both also have high D/H ratios.

astro-ph.GA↗

arXiv2012

Probing the physical and chemical structure of the CS core in LDN 673. Multitransitional and continuum observations

High-angular resolution observations of dense molecular cores show that these cores can be clumpier at smaller scales, and that some of these clumps can also be unbound or transient. The use of chemical models of the evolution of the molecular gas provides a way to probe the physical properties of the clouds. We study the properties of the clump and inter-clump medium in the starless CS core in LDN 673 by carrying out a molecular line survey with the IRAM 30-m telescope toward two clumps and two inter-clump positions. We also observed the 1.2-mm continuum with the MAMBO-II bolometer at IRAM. The dust continuum map shows four condensations, three of them centrally peaked, coinciding with previously identified sub-millimetre sources. We confirm that the denser clump of the region, $n\sim3.6 \times10^5$\cmt, is also the more chemically evolved, and it could still undergo further fragmentation. The inter-clump medium positions are denser than previously expected, likely $n\sim1\times10^3$--1$\times10^4$\cmt\ due to contamination, and are chemically young, similar to the gas in the lower density clump position. We argue that the density contrast between these positions and their general young chemical age would support the existence of transient clumps in the lower density material of the core. We were also able to find reasonable fits of the observationally derived chemical abundances to models of the chemistry of transient clumps.

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arXiv2011

On the Formation of CO2 and Other Interstellar Ices

We investigate the formation and evolution of interstellar dust-grain ices under dark-cloud conditions, with a particular emphasis on CO2. We use a three-phase model (gas/surface/mantle) to simulate the coupled gas--grain chemistry, allowing the distinction of the chemically-active surface from the ice layers preserved in the mantle beneath. The model includes a treatment of the competition between barrier-mediated surface reactions and thermal-hopping processes. The results show excellent agreement with the observed behavior of CO2, CO and water ice in the interstellar medium. The reaction of the OH radical with CO is found to be efficient enough to account for CO2 ice production in dark clouds. At low visual extinctions, with dust temperatures ~12 K, CO2 is formed by direct diffusion and reaction of CO with OH; we associate the resultant CO2-rich ice with the observational polar CO2 signature. CH4 ice is well correlated with this component. At higher extinctions, with lower dust temperatures, CO is relatively immobile and thus abundant; however, the reaction of H and O atop a CO molecule allows OH and CO to meet rapidly enough to produce a CO:CO2 ratio in the range ~2--4, which we associate with apolar signatures. We suggest that the observational apolar CO2/CO ice signatures in dark clouds result from a strongly segregated CO:H2O ice, in which CO2 resides almost exclusively within the CO component. Observed visual-extinction thresholds for CO2, CO and H2O are well reproduced by depth-dependent models. Methanol formation is found to be strongly sensitive to dynamical timescales and dust temperatures.

astro-ph.GA↗

arXiv2008

Modeling the Lukewarm Corino Phase - is L1527 unique?

Sakai et al. have observed long-chain unsaturated hydrocarbons and cyanopolyynes in the low-mass star-forming region L1527, and have attributed this result to a gas-phase ion-molecule chemistry, termed ``Warm Carbon Chain Chemistry'', which occurs during and after the evaporation of methane from warming grains. The source L1527 is an envelope surrounding a Class 0/I protostar with regions that possess a slightly elevated temperature of ~30 K. The molecules detected by Sakai et al. are typically associated only with dark molecular clouds, and not with the more evolved hot corino phase. In order to determine if L1527 is chemically distinct from a dark cloud, we compute models including various degrees of heating. The results indicate that the composition of L1527 is somewhat more likely to be due to ``Warm Carbon Chain Chemistry'' than to be a remnant of a colder phase. If so, the molecular products provide a signature of a previously uncharacterized early phase of low mass star formation, which can be characterized as a ``lukewarm'' corino. We also include predictions for other molecular species that might be observed toward candidate lukewarm corino sources. Although our calculations show that unsaturated hydrocarbons and cyanopolyynes can be produced in the gas phase as the grains warm up to 30 K, they also show that such species do not disappear rapidly from the gas as the temperature reaches 200 K, implying that such species might be detected in hot corinos and hot cores.

astro-ph↗

arXiv2008

Complex Chemistry in Star-Forming Regions: An Expanded Gas-Grain Warm-up Chemical Model

Gas-phase processes were long thought to be the key formation mechanisms for complex organic molecules in star-forming regions. However, recent experimental and theoretical evidence has cast doubt on the efficiency of such processes. Grain-surface chemistry is frequently invoked as a solution, but until now there have been no quantitative models taking into account both the high degree of chemical complexity and the evolving physical conditions of star-forming regions. Here, we introduce a new gas-grain chemical network, wherein a wide array of complex species may be formed by reactions involving radicals. The radicals we consider (H, OH, CO, HCO, CH3, CH3O, CH2OH, NH and NH2) are produced primarily by cosmic ray-induced photodissociation of the granular ices formed during the colder, earlier stages of evolution. The gradual warm-up of the hot core is crucial to the formation of complex molecules, allowing the more strongly-bound radicals to become mobile on grain surfaces. This type of chemistry is capable of reproducing the high degree of complexity seen in Sgr B2(N), and can explain the observed abundances and temperatures of a variety of previously detected complex organic molecules, including structural isomers. Many other complex species are predicted by this model, and several of these species may be detectable in hot cores. Differences in the chemistry of high- and low-mass star-formation are also addressed; greater chemical complexity is expected where evolution timescales are longer.

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arXiv2007

Forming an Early O-type Star Through Gas Accretion?

We present high angular resolution ($\sim$ 3$''$) and sensitive 1.3 mm continuum, cyanogen (CN) and vinyl cyanide (C$_2$H$_3$CN) line observations made with the Submillimeter Array (SMA) toward one of most highly obscured objects of the W51 IRS2 region, W51 North. We find that the CN line exhibits a pronounced inverse P-Cygni profile indicating that the molecular gas is infalling inwards this object with a mass accretion rate between 4 and 7 $\times$ 10$^{-2}$ M$_\odot$ yr$^{-1}$. The C$_2$H$_3$CN traces an east-west rotating molecular envelope that surrounds either a single obscured (proto)star with a kinematic mass of 40 M$_{\odot}$ or a small central cluster of B-type stars and that is associated with a compact high velocity bipolar outflow traced by H$_2$O masers and SiO molecular emission. We thus confirm that the W51 North region is part of the growing list of young massive star forming regions that have been associated with infalling motions and with large mass accretion rates ($\sim$ 10$^{-2}$ -- 10$^{-4}$), strengthening the evidence for massive stars forming with very high accretion rates sufficient to quench the formation of an UCHII region.

astro-ph↗

arXiv2007

Molecular Evolution and Star Formation: From Prestellar Cores to Protostellar Cores

We investigate molecular evolution in a star-forming core that is initially a hydrostatic starless core and collapses to form a low-mass protostar. The results of a one-dimensional radiation-hydrodynamics calculation are adopted as a physical model of the core. We first derive radii at which CO and large organic species sublimate. CO sublimation in the central region starts shortly before the formation of the first hydrostatic core. When the protostar is born, the CO sublimation radius extends to 100 AU, and the region inside $\lesssim 10$ AU is hotter than 100 K, at which some large organic species evaporate. We calculate the temporal variation of physical parameters in infalling shells, in which the molecular evolution is solved using an updated gas-grain chemical model to derive the spatial distribution of molecules in a protostellar core. The shells pass through the warm region of $10 -100$ K in several $\times$ $10^4$ yr, and fall into the central star $\sim 100$ yr after they enter the region where $T \gtrsim 100$ K. We find that large organic species are formed mainly via grain-surface reactions at temperatures of $20 -40$ K and then desorbed into the gas-phase at their sublimation temperatures. Carbon-chain species can be formed by a combination of gas-phase reactions and grain-surface reactions following the sublimation of CH$_4$. Our model also predicts that CO$_2$ is more abundant in isolated cores, while gas-phase large organic species are more abundant in cores embedded in ambient clouds.

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