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Register a new userOn the Formation of Deuterated Methyl Formate in Hot Corinos
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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.
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Methyl carbamate CH$_3$OC(O)NH$_2$ is an isomer of glycine. Quantum chemical analyses show that methyl carbamate is more stable isomer than glycine. Because of this, there could be a higher chance for methyl carbamte to exist in the interstellar medium as compared to glycine. Despite immense searches, till now glycine has not been detected in the ISM, therefore it is worthwhile to search its isomer methyl carbamate. In this paper, we present the constraints of methyl carbamate formation under the interstellar conditions. Large complex organic molecules are favorably produced in hot-corino environments of low mass protostars. We for the first time carried out astrochemical modeling focusing on the formation of methyl carbamate in physical conditions similar to hot-corino objects. Consequently, we examined ALMA archival data for existing spectral line observations toward hot corinos NGC1333 IRAS 4A2 and IRAS 16293B. Within the common spectral range towards these sources, we found three features are possibly related to the spectral transitions of methyl carbamate and consequently estimate the upper limit of column densities. Results of chemical modeling are consistent with the observational upper limit of estimated column density/abundance toward the sources. This may hint the validation of the proposed formation mechanism. Future observations using telescope like ngVLA may confirm the presence of MC toward the hot corinos.
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.
We report the first detection in space of the two doubly deuterated isotopologues of methyl acetylene. The species CHD2CCH and CH2DCCD were identified in the dense core L483 through nine and eight, respectively, rotational lines in the 72-116 GHz range using the IRAM 30m telescope. The astronomical frequencies observed here were combined with laboratory frequencies from the literature measured in the 29-47 GHz range to derive more accurate spectroscopic parameters for the two isotopologues. We derive beam-averaged column densities of (2.7 +/- 0.5)e12 cm-2 for CHD2CCH and (2.2 +/- 0.4)e12 cm-2 for CH2DCCD, which translate to abundance ratios CH3CCH/CHD2CCH = 34 +/- 10 and CH3CCH/CH2DCCD = 42 +/- 13. The doubly deuterated isotopologues of methyl acetylene are only a few times less abundant than the singly deuterated ones, concretely around 2.4 times less abundant than CH3CCD. The abundances of the different deuterated isotopologues with respect to CH3CCH are reasonably accounted for by a gas-phase chemical model in which deuteration occurs from the precursor ions C3H6D+ and C3H5D+, when the ortho-to-para ratio of molecular hydrogen is sufficiently low. This points to gas-phase chemical reactions, rather than grain-surface processes, as responsible for the formation and deuterium fractionation of CH3CCH in L483. The abundance ratios CH2DCCH/CH3CCD = 3.0 +/- 0.9 and CHD2CCH/CH2DCCD = 1.25 +/- 0.37 observed in L483 are consistent with the statistically expected values of three and one, respectively, with the slight overabundance of CHD2CCH compared to CH2DCCD being well explained by the chemical model.
Methyl formate in its first torsionally excited state (vt=1 at 131 cm-1) is detected for the first time toward W51 e2. All transitions from excited methyl formate within the observed spectral range are actually detected (82 transitions) and no strong lines are missing. The column density of the excited state is comparable to that of the ground state. For a source size of 7 we find that Trot = 104 +/- 14 K and N = 9.4 +4.0/-2.8 x 10^16 cm-2 for the excited state and Trot = 176 +/- 24 K and N = 1.7 +.2/-.2 x 10^17 cm-2 for the ground state. Lines from ethyl cyanide in its two first excited states (vt=1, torsion mode at 212 cm-1) and (vb=1, CCN in-plane bending mode at 206 cm-1) are also present in the observed spectrum. However blending problems prevent a precise estimate of its abundance. With regard to the number of lines of excited methyl formate and ethyl cyanide detected in W51 e2, it appears that excited states of large molecules certainly account for a large number of unidentified lines in spectral survey of molecular clouds.
After almost 20 years of hunting, only about a dozen hot corinos, hot regions enriched in interstellar complex organic molecules (iCOMs), are known. Of them, many are binary systems with the two components showing drastically different molecular spectra. Two obvious questions arise. Why are hot corinos so difficult to find and why do their binary components seem chemically different? The answer to both questions could be a high dust opacity that would hide the molecular lines. To test this hypothesis, we observed methanol lines at centimeter wavelengths, where dust opacity is negligible, using the Very Large Array interferometer. We targeted the NGC 1333 IRAS 4A binary system, for which one of the two components, 4A1, has a spectrum deprived of iCOMs lines when observed at millimeter wavelengths, while the other component, 4A2, is very rich in iCOMs. We found that centimeter methanol lines are similarly bright toward 4A1 and 4A2. Their non-LTE analysis indicates gas density and temperature ($geq2times10^6$ cm$^{-3}$ and 100--190 K), methanol column density ($sim10^{19}$ cm$^{-2}$) and extent ($sim$35 au in radius) similar in 4A1 and 4A2, proving that both are hot corinos. Furthermore, the comparison with previous methanol line millimeter observations allows us to estimate the optical depth of the dust in front of 4A1 and 4A2, respectively. The obtained values explain the absence of iCOMs line emission toward 4A1 at millimeter wavelengths and indicate that the abundances toward 4A2 are underestimated by $sim$30%. Therefore, centimeter observations are crucial for the correct study of hot corinos, their census, and their molecular abundances.
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