arXiv subjects

R. T. Garrod

Publications and source records attributed to R. T. Garrod.

48 records · Page 3Linked to original sources

arXiv2016

The ALMA-PILS survey: First detections of deuterated formamide and deuterated isocyanic acid in the interstellar medium

Formamide (NH$_2$CHO) has previously been detected in several star-forming regions and is thought to be a precursor for different prebiotic molecules. Its formation mechanism is still debated, however. Observations of formamide, related species and their isopotologues may provide useful clues to the chemical pathways leading to their formation. The Protostellar Interferometric Line Survey (PILS) represents an unbiased high angular resolution and sensitivity spectral survey of the low-mass protostellar binary IRAS 16293-2422 with the Atacama Large Millimeter/submillimeter Array (ALMA). We detect for the first time the three singly deuterated forms of NH$_2$CHO (NH$_2$CDO, cis- and trans-NHDCHO) as well as DNCO towards the component B of this binary source. The images reveal that the different isotopologues are all present in the same region. Based on observations of the $^{13}$C isotopologues of formamide and a standard $^{12}$C/$^{13}$C ratio, the deuterium fractionation is found to be similar for the three different forms with a value of about 2%. The DNCO/HNCO ratio is also comparable to the D/H ratio of formamide ($\sim$1%). These results are in agreement with the hypothesis that NH$_2$CHO and HNCO are chemically related through grain surface formation.

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arXiv2016

Spectroscopic study and astronomical detection of doubly 13C-substituted ethyl cyanide

We have performed a spectral line survey called EMoCA toward Sagittarius B2(N) between 84 and 114 GHz with ALMA. Line intensities of the main isotopic species of ethyl cyanide and its singly 13C-substituted isotopomers observed toward the hot molecular core Sgr B2(N2) suggest that the doubly 13C-substituted isotopomers should be detectable also. We want to determine the spectroscopic parameters of all three doubly 13C-substituted isotopologues of ethyl cyanide to search for them in our ALMA data. We investigated the laboratory rotational spectra of the three species between 150 and 990 GHz. We searched for emission lines produced by these species in the ALMA spectrum of Sgr B2(N2). We modeled their emission as well as the emission of the 12C and singly 13C-substituted isotopologues assuming local thermodynamic equilibrium. We identified more than 5000 rotational transitions, pertaining to more than 3500 different transition frequencies, in the laboratory for each of the three isotopomers. The quantum numbers reach J ~ 115 and K_a ~ 35, resulting in accurate spectroscopic parameters and accurate rest frequency calculations beyond 1000 GHz for strong to moderately weak transitions of either isotopomer. All three species are unambiguously detected in our ALMA data. The 12C/13C column density ratio of the isotopomers with one 13C atom to the ones with two 13C atoms is about 25. Ethyl cyanide is the second molecule after methyl cyanide for which isotopologues containing two 13C atoms have been securely detected in the interstellar medium. The model of our ethyl cyanide data suggests that we should be able to detect vibrational satellites of the main species up to at least v_19 = 1 at 1130 K and up to v_13 + v_21 = 2 at 600 K for the isotopologues with one 13C atom in our present ALMA data. Such satellites may be too weak to be identified unambiguously for isotopologues with two 13C atoms.

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arXiv2015

Exploring molecular complexity with ALMA (EMoCA): Alkanethiols and alkanols in Sagittarius B2(N2)

Over the past five decades, radio astronomy has shown that molecular complexity is a natural outcome of interstellar chemistry, in particular in star forming regions. However, the pathways that lead to the formation of complex molecules are not completely understood and the depth of chemical complexity has not been entirely revealed. In addition, the sulfur chemistry in the dense interstellar medium is not well understood. We want to know the relative abundances of alkanethiols and alkanols in the Galactic Center source Sagittarius B2(N2), the northern hot molecular core in Sgr B2(N), whose relatively small line widths are favorable for studying the molecular complexity in space. We investigated spectroscopic parameter sets that were able to reproduce published laboratory rotational spectra of ethanethiol and studied effects that modify intensities in the predicted rotational spectrum of ethanol. We used the Atacama Large Millimeter Array (ALMA) in its Cycles~0 and 1 for a spectral line survey of Sagittarius B2(N) between 84 and 114.4 GHz. These data were analyzed by assuming local thermodynamic equilibrium (LTE) for each molecule. Our observations are supplemented by astrochemical modeling; a new network is used for the first time that includes reaction pathways for alkanethiols. The column density ratios involving methanol, ethanol, and methanethiol in Sgr B2(N2) are similar to values reported for Orion KL, but those involving ethanethiol are significantly different and suggest that the detection of ethanethiol reported toward Orion KL is uncertain. Our chemical model presently does not permit the prediction of sufficiently accurate column densities of alkanethiols or their ratios among alkanethiols and alkanols. Therefore, additional observational results are required to establish the level of C2H5SH in the dense and warm interstellar medium with certainty.

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arXiv2015

Exploring Molecular Complexity with ALMA (EMoCA): Deuterated complex organic molecules in Sagittarius B2(N2)

Deuteration is a powerful tracer of the history of the cold prestellar phase in star forming regions. Apart from methanol, little is known about deuterium fractionation of complex organic molecules in the interstellar medium, especially in high mass star forming regions. We use a spectral line survey performed with ALMA to search for deuterated complex organic molecules toward the hot molecular core Sgr B2(N2). Population diagrams and integrated intensity maps are constructed to fit rotational temperatures and emission sizes for each molecule. Column densities are derived by modelling the full spectrum under the LTE assumption. The results are compared to predictions of two astrochemical models that treat the deuteration process. We report the detection of CH2DCN toward Sgr B2(N2) with a deuteration level of 0.4%, and tentative detections of CH2DOH, CH2DCH2CN, the chiral molecule CH3CHDCN, and DC3N with levels in the range 0.05%-0.12%. A stringent deuteration upper limit is obtained for CH3OD (<0.07%). Upper limits in the range 0.5-1.8% are derived for the three deuterated isotopologues of vinyl cyanide, the four deuterated species of ethanol, and CH2DOCHO. Ethyl cyanide is less deuterated than methyl cyanide by at least a factor five. Except for methyl cyanide, the measured deuteration levels lie at least a factor four below the predictions of current astrochemical models. The deuteration levels in Sgr B2(N2) are also lower than in Orion KL by a factor of a few up to a factor ten. The discrepancy between the deuteration levels of Sgr B2(N2) and the predictions of chemical models, and the difference between Sgr B2(N2) and Orion KL may both be due to the higher kinetic temperatures that characterize the Galactic Center region compared to nearby clouds. Alternatively, they may result from a lower overall abundance of deuterium itself in the Galactic Center region by up to a factor ten.

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arXiv2014

Star formation in Chamaeleon I and III: a molecular line study of the starless core population

The Chamaeleon clouds are excellent targets for low-mass star formation studies. Cha I and II are actively forming stars while Cha III shows no sign of ongoing star formation. We aim to determine the driving factors that have led to the very different levels of star formation activity in Cha I and III and examine the dynamical state and possible evolution of the starless cores within them. Observations were performed in various molecular transitions with APEX and Mopra. Five cores are gravitationally bound in Cha I and one in Cha III. The infall signature is seen toward 8-17 cores in Cha I and 2-5 cores in Cha III, which leads to a range of 13-28% of the cores in Cha I and 10-25% of the cores in Cha III that are contracting and may become prestellar. Future dynamical interactions between the cores will not be dynamically significant in either Cha I or III, but the subregion Cha I North may experience collisions between cores within ~0.7 Myr. Turbulence dissipation in the cores of both clouds is seen in the high-density tracers N2H+ 1-0 and HC3N 10-9. Evidence of depletion in the Cha I core interiors is seen in the abundance distributions of C17O, C18O, and C34S. Both contraction and static chemical models indicate that the HC3N to N2H+ abundance ratio is a good evolutionary indicator in the prestellar phase for both gravitationally bound and unbound cores. In the framework of these models, we find that the cores in Cha III and the southern part of Cha I are in a similar evolutionary stage and are less chemically evolved than the central region of Cha I. The measured HC3N/N2H+ abundance ratio and the evidence for contraction motions seen towards the Cha III starless cores suggest that Cha III is younger than Cha I Centre and that some of its cores may form stars in the future. The cores in Cha I South may on the other hand be transient structures. (abridged)

astro-ph.GA↗

arXiv2009

Formation rates of complex organics in UV irradiated CH3OH-rich ices I: Experiments

(Abridged) Gas-phase complex organic molecules are commonly detected in the warm inner regions of protostellar envelopes. Recent models show that photochemistry in ices followed by desorption may explain the observed abundances. This study aims to experimentally quantify the broad-band UV-induced production rates of complex organics in CH3OH-rich ices at 20-70 K under ultra-high vacuum conditions. The reaction products are mainly identified by RAIRS and TPD experiments. Complex organics are readily formed in all experiments, both during irradiation and during a slow warm-up of the ices to 200 K after the UV lamp is turned off. The relative abundances of photoproducts depend on the UV fluence, the ice temperature, and whether pure CH3OH ice or CH3OH:CH4/CO ice mixtures are used. C2H6, CH3CHO, CH3CH2OH, CH3OCH3, HCOOCH3, HOCH2CHO and (CH2OH)2 are all detected in at least one experiment. The derived product-formation yields and their dependences on different experimental parameters, such as the initial ice composition, are used to estimate the CH3OH photodissociation branching ratios in ice and the relative diffusion barriers of the formed radicals. The experiments show that ice photochemistry in CH3OH ices is efficient enough to explain the observed abundances of complex organics around protostars and that ratios of complex molecules can be used to constrain their formation pathway.

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arXiv2009

Increased complexity in interstellar chemistry: Detection and chemical modeling of ethyl formate and n-propyl cyanide in Sgr B2(N)

In recent years, organic molecules of increasing complexity have been found toward the prolific Galactic center source Sagittarius B2. We wish to explore the degree of complexity that the interstellar chemistry can reach in star-forming regions. We carried out a complete line survey of the hot cores Sgr B2(N) and (M) with the IRAM 30 m telescope in the 3 mm range. We analyzed this spectral survey in the LTE approximation. We modeled the emission of all known molecules simultaneously, which allows us to search for less abundant, more complex molecules. We compared the derived column densities with the predictions of a coupled gas-phase and grain-surface chemical code. We report the first detection in space of ethyl formate (C2H5OCHO) and n-propyl cyanide (C3H7CN) toward Sgr B2(N). The abundances of ethyl formate and n-propyl cyanide relative to H2 are estimated to be 3.6e-9 and 1.0e-9, respectively. Our chemical modeling suggests that the sequential, piecewise construction of ethyl and n-propyl cyanide from their constituent functional groups on the grain surfaces is their most likely formation route. Ethyl formate is primarily formed on the grains by adding CH3 to functional-group radicals derived from methyl formate, although ethanol may also be a precursor. The detection in Sgr B2(N) of the next stage of complexity in two classes of complex molecule, esters and alkyl cyanides, suggests that greater complexity in other classes of molecule may be present in the interstellar medium. {Abridged}

astro-ph.GA↗

arXiv2008

A new modified-rate approach for gas-grain chemical simulations

Understanding grain-surface processes is crucial to interpreting the chemistry of the ISM. However, accurate surface chemistry models are computationally expensive and are difficult to integrate with gas-phase simulations. A new modified-rate method for solving grain-surface chemical systems is presented. Its purpose is accurately to model highly complex systems that can otherwise only be treated using the sometimes inadequate rate-equation approach. In contrast to previous rate-modification techniques, the functional form of the surface production rates was modified, and not simply the rate coefficient. This form is appropriate to the extreme "small-grain" limit, and can be verified using an analytical master-equation approach. Various further modifications were made to this basic form, to account for competition between processes, to improve estimates of surface occupation probabilities, and to allow a switch-over to the normal rate equations where these are applicable. The new method was tested against systems solved previously using exact techniques. Even the simplest method is quite accurate, and a great improvement over rate equations. Further modifications allow the master-equation results to be reproduced exactly for the methanol-producing system, within computational accuracy. Small discrepancies arise when non-zero activation energies are assumed for the methanol system, which result from complex reaction-competition processes that cannot be resolved easily without using exact methods. Inaccuracies in computed abundances are never greater than a few tens of percent, and typically of the order of one percent, in the most complex systems tested. Implementation of the method in simple networks, including hydrogen-only systems, is trivial, whilst the results are highly accurate.

astro-ph↗

arXiv2007

Non-thermal desorption from interstellar dust grains via exothermic surface reactions

Aims: The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely contrained by theoretical work. Results: Our results show that the chemistry of dark clouds is altered slightly at times up to 10^6 yr, mainly by the enhancement in the gas-phase abundances of hydrogen-rich species such as methanol that are formed on grain surfaces. At later times, however, there is a rather strong change. Instead of the continuing accretion of most gas-phase species onto dust particles, a steady-state is reached for both gas-phase and grain-surface species, with significant abundances for the former. Nevertheless, most of the carbon is contained in an undetermined assortment of heavy surface hydrocarbons. Conclusions: The desorption mechanism discussed here will be better constrained by observational data on pre-stellar cores, where a significant accretion of species such as CO has already occurred.

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arXiv2006

Dense and diffuse gas in dynamically active clouds

We investigate the chemical and observational implications of repetitive transient dense core formation in molecular clouds. We allow a transient density fluctuation to form and disperse over a period of 1 Myr, tracing its chemical evolution. We then allow the same gas immediately to undergo further such formation and dispersion cycles. The chemistry of the dense gas in subsequent cycles is similar to that of the first, and a limit cycle is reached quickly (2 - 3 cycles). Enhancement of hydrocarbon abundances during a specific period of evolution is the strongest indicator of previous dynamical history. The molecular content of the diffuse background gas in the molecular cloud is expected to be strongly enhanced by the core formation and dispersion process. Such enhancement may remain for as long as 0.5 Myr. The frequency of repetitive core formation should strongly determine the level of background molecular enhancement. We also convolve the emission from a synthesised dark cloud, comprised of ensembles of transient dense cores. We find that the dynamical history of the gas, and therefore the chemical state of the diffuse inter-core medium, may be determined if a sufficient sample of cores is present in an ensemble. Molecular ratios of key hydrocarbons with SO and SO2 are crucial to this distinction. Only surveys with great enough angular resolution to resolve individual cores, or very small groupings, are expected to show evidence of repetitive dynamical processing. The existence of non-equilibrium chemistry in the diffuse background may have implications for the initial conditions used in chemical models. Observed variations in the chemistries of diffuse and translucent regions may be explained by lines of sight which intersect a number of molecular cloud cores in various stages of evolution.

astro-ph↗

arXiv2006

Formation of methyl formate and other organic species in the warm-up phase of hot molecular cores

Aims: The production of saturated organic molecules in hot cores and corinos is not well understood. The standard approach is to assume that, as temperatures heat up during star formation, methanol and other species evaporate from grain surfaces and undergo a warm gas-phase chemistry at 100 K or greater to produce species such as methyl formate, dimethyl ether, and others. But a series of laboratory results shows that protonated ions, typical precursors to final products in ion-molecule schemes, tend to fragment upon dissociative recombination with electrons rather than just ejecting a hydrogen atom. Moreover, the specific proposed reaction to produce protonated methyl formate is now known not to occur at all. Methods: We utilize a gas-grain chemical network to probe the chemistry of the relatively ignored stage of hot core evolution during which the protostar switches on and the temperature of the surrounding gas and dust rises from 10 K to over 100 K. During this stage, surface chemistry involving heavy radicals becomes more important as surface hydrogen atoms tend to evaporate rather than react. Results: Our results show that complex species such as methyl formate, formic acid, and dimethyl ether can be produced in large abundance during the protostellar switch-on phase, but that both grain-surface and gas-phase processes help to produce most species. The longer the timescale for protostellar switch-on, the more important the surface processes.

astro-ph↗

arXiv2005

Molecular Clouds as Ensembles of Transient Cores

We construct models of molecular clouds that are considered as ensembles of transient cores. Each core is assumed to develop in the background gas of the cloud, grow to high density and decay into the background. The chemistry in each core responds to the dynamical state of the gas and to the gas-dust interaction. Ices are deposited on the dust grains in the core's dense phase, and this material is returned to the gas as the core expands to low density. The cores of the ensemble number typically one thousand and are placed randomly in position within the cloud, and are assigned a random evolutionary phase. The models are used to generate molecular line contour maps of a typical dark cloud. These maps are found to represent extremely well the characteristic features of observed maps of the dark cloud L673, which has been observed at both low and high resolutions. The computed maps are found to exhibit the general morphology of the observed maps, and to generate similar sizes of emitting regions, molecular column densities, and the separations between peaks of emissions of various molecular species. The models give insight into the nature of molecular clouds and the dynamical processes occurring within them, and significantly constrain dynamical and chemical processes in the interstellar medium.

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