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Register a new userTIMASSS : The IRAS16293-2422 Millimeter And Submillimeter Spectral Survey: Tentative Detection of Deuterated Methyl Formate (DCOOCH3)
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Karine Demyk
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High deuterium fractionation is observed in various types of environment such as prestellar cores, hot cores and hot corinos. It has proven to be an efficient probe to study the physical and chemical conditions of these environments. The study of the deuteration of different molecules helps us to understand their formation. This is especially interesting for complex molecules such as methanol and bigger molecules for which it may allow to differentiate between gas-phase and solid-state formation pathways. Methanol exhibits a high deuterium fractionation in hot corinos. Since CH3OH is thought to be a precursor of methyl formate we expect that deuterated methyl formate is produced in such environments. We have searched for the singly-deuterated isotopologue of methyl formate, DCOOCH3, in IRAS 16293-2422, a hot corino well-known for its high degree of methanol deuteration. We have used the IRAM/JCMT unbiased spectral survey of IRAS 16293-2422 which allows us to search for the DCOOCH3 rotational transitions within the survey spectral range (80-280 GHz, 328-366 GHz). The expected emission of deuterated methyl formate is modelled at LTE and compared with the observations.} We have tentatively detected DCOOCH3 in the protostar IRAS 16293-2422. We assign eight lines detected in the IRAM survey to DCOOCH3. Three of these lines are affected by blending problems and one line is affected by calibration uncertainties, nevertheless the LTE emission model is compatible with the observations. A simple LTE modelling of the two cores in IRAS 16293-2422, based on a previous interferometric study of HCOOCH3, allows us to estimate the amount of DCOOCH3 in IRAS 16293-2422. Adopting an excitation temperature of 100 K and a source size of 2arcsec and 1farcs5 for the A and B cores, respectively, we find that N(A,DCOOCH3) = N(B,DCOOCH3) ~ 6.10^14 /cm2. The derived deuterium fractionation is ~ 15%, consistent with values for other deuterated species in this source and much greater than that expected from the deuterium cosmic abundance. DCOOCH3, if its tentative detection is confirmed, should now be considered in theoretical models that study complex molecule formation and their deuteration mechanisms. Experimental work is also needed to investigate the different chemical routes leading to the formation of deuterated methyl formate.
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While unbiased surveys observable from ground-based telescopes have previously been obtained towards several high mass protostars, very little exists on low mass protostars. To fill up this gap, we carried out a complete spectral survey of the bands at 3, 2, 1 and 0.8 mm towards the solar type protostar IRAS16293-2422. The observations covered about 200,GHz and were obtained with the IRAM-30m and JCMT-15m telescopes. Particular attention was devoted to the inter-calibration of the obtained spectra with previous observations. All the lines detected with more than 3 sigma and free from obvious blending effects were fitted with Gaussians to estimate their basic kinematic properties. More than 4000 lines were detected (with sigma geq 3) and identified, yielding a line density of approximatively 20 lines per GHz, comparable to previous surveys in massive hot cores. The vast majority (~2/3) of the lines are weak and due to complex organic molecules. The analysis of the profiles of more than 1000 lines belonging 70 species firmly establishes the presence of two distinct velocity components, associated with the two objects, A and B, forming the IRAS16293-2422 binary system. In the source A, the line widths of several species increase with the upper level energy of the transition, a behavior compatible with gas infalling towards a ~1 Mo object. The source B, which does not show this effect, might have a much lower central mass of ~0.1 Mo. The difference in the rest velocities of both objects is consistent with the hypothesis that the source B rotates around the source A. This spectral survey, although obtained with single-dish telescope with a low spatial resolution, allows to separate the emission from 2 different components, thanks to the large number of lines detected. The data of the survey are public and can be retrieved on the web site http://www-laog.obs.ujf-grenoble.fr/heberges/timasss.
The rotational spectrum of the higher-energy trans conformational isomer of methyl formate has been assigned for the first time using several pulsed-jet Fourier transform microwave spectrometers in the 6-60 GHz frequency range. This species has also been sought toward the Sagittarius B2(N) molecular cloud using the publicly available PRIMOS survey from the Green Bank Telescope. We detect seven absorption features in the survey that coincide with laboratory transitions of trans-methyl formate, from which we derive a column density of 3.1 (+2.6, -1.2) times 10^13 cm-2 and a rotational temperature of 7.6 pm 1.5 K. This excitation temperature is significantly lower than that of the more stable cis conformer in the same source but is consistent with that of other complex molecular species recently detected in Sgr B2(N). The difference in the rotational temperatures of the two conformers suggests that they have different spatial distributions in this source. As the abundance of trans-methyl formate is far higher than would be expected if the cis and trans conformers are in thermodynamic equilibrium, processes that could preferentially form trans-methyl formate in this region are discussed. We also discuss measurements that could be performed to make this detection more certain. This manuscript demonstrates how publicly available broadband radio astronomical surveys of chemically rich molecular clouds can be used in conjunction with laboratory rotational spectroscopy to search for new molecules in the interstellar medium.
Methyl formate, HCOOCH$_3$, and many of its isotopologues have been detected in astrophysical regions with considerable abundances. However, the recipe for the formation of this molecule and its isotopologues is not yet known. In this work, we attempt to investigate, theoretically, the successful recipe for the formation of interstellar HCOOCH$_3$ and its deuterated isotopologues. We used the gas-grain chemical model, UCLCHEM, to examine the possible routes of formation of methyl formate on grain surfaces and in the gas-phase in low-mass star-forming regions. Our models show that radical-radical association on grains are necessary to explain the observed abundance of DCOOCH$_3$ in the protostar IRAS~16293--2422. H-D substitution reactions on grains significantly enhance the abundances of HCOOCHD$_2$, DCOOCHD$_2$, and HCOOCD$_3$. The observed abundance of HCOOCHD$_2$ in IRAS 16293--2422 can only be reproduced if H-D substitution reactions are taken into account. However, HCOOCH$_2$D remain underestimated in all of our models. The deuteration of methyl formate appears to be more complex than initially thought. Additional studies, both experimentally and theoretically, are needed for a better understanding of the interstellar formation of these species.
The HDO/H2O ratio is a powerful diagnostic to understand the evolution of water from the first stages of star formation to the formation of planets and comets. Our aim is to determine precisely the abundance distribution of HDO towards the low-mass protostar IRAS16293-2422 and learn more about the water formation mechanisms by determining the HDO/H2O abundance ratio. A spectral survey of the source IRAS16293-2422 was carried out in the framework of the CHESS Herschel Key program with the HIFI instrument, allowing the detection of numerous HDO lines. Other transitions have been observed previously with ground-based telescopes. The spherical Monte Carlo radiative transfer code RATRAN was used to reproduce the observed line profiles of HDO by assuming an abundance jump. To determine the H2O abundance throughout the envelope, a similar study was made of the H2-18O observed lines, as the H2O main isotope lines are contaminated by the outflows. We derive an inner HDO abundance of 1.7e-7 and an outer HDO abundance of 8e-11. To reproduce the HDO absorption lines, it is necessary to add an absorbing layer in front of the envelope. It may correspond to a water-rich layer created by the photodesorption of the ices at the edges of the molecular cloud. The HDO/H2O ratio is ~1.4-5.8% in the hot corino whereas it is ~0.2-2.2% in the outer envelope. It is estimated at ~4.8% in the added absorbing layer. Although it is clearly higher than the cosmic D/H abundance, the HDO/H2O ratio remains lower than the D/H ratio derived for other deuterated molecules observed in the same source. The similarity of the ratios derived in the hot corino and in the added absorbing layer suggests that water formed before the gravitational collapse of the protostar, contrary to formaldehyde and methanol, which formed later once the CO molecules had depleted on the grains.
Although water is an essential and widespread molecule in star-forming regions, its chemical formation pathways are still not very well constrained. Observing the level of deuterium fractionation of OH, a radical involved in the water chemical network, is a promising way to infer its chemical origin. We aim at understanding the formation mechanisms of water by investigating the origin of its deuterium fractionation. This can be achieved by observing the abundance of OD towards the low-mass protostar IRAS16293-2422, where the HDO distribution is already known. Using the GREAT receiver on board SOFIA, we observed the ground-state OD transition at 1391.5 GHz towards the low-mass protostar IRAS16293-2422. We also present the detection of the HDO 111-000 line using the APEX telescope. We compare the OD/HDO abundance ratio inferred from these observations with the predictions of chemical models. The OD line is detected in absorption towards the source continuum. This is the first detection of OD outside the solar system. The SOFIA observation, coupled to the observation of the HDO 111-000 line, provides an estimate of the abundance ratio OD/HDO ~ 17-90 in the gas where the absorption takes place. This value is fairly high compared with model predictions. This may be reconciled if reprocessing in the gas by means of the dissociative recombination of H2DO+ further fractionates OH with respect to water. The present observation demonstrates the capability of the SOFIA/GREAT instrument to detect the ground transition of OD towards star-forming regions in a frequency range that was not accessible before. Dissociative recombination of H2DO+ may play an important role in setting a high OD abundance. Measuring the branching ratios of this reaction in the laboratory will be of great value for chemical models.
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