This paper presents a systematic survey of the deuterated and 13C isotopologues of a variety of oxygen-bearing complex organic molecules on Solar System scales toward the protostar IRAS 16293-2422B. We use the data from an unbiased molecular line survey between 329 and 363 GHz from the Atacama Large Millimeter/submillimeter Array (ALMA). The observations probe scales of 60 AU where most of the organic molecules have sublimated off dust grains and are present in the gas-phase. The complex organic molecules can be divided into two groups with one group, the simpler species, showing a D/H ratio of approximately 2% and the other, the more complex species, D/H ratios of 4-8%. This division may reflect the formation time of each species in the ices before or during warm-up/infall of material through the protostellar envelope. No significant differences are seen in the deuteration of different functional groups for individual species, possibly a result of the short time-scale for infall through the innermost warm regions where exchange reactions between different species may be taking place. The species show differences in excitation temperatures between 125 K and 300 K. This likely reflects the binding energies/sublimation temperatures of the individual species, in good agreement to what has previously been found for high-mass sources. For dimethyl ether, the 12C/13C ratio is found to be lower by up to a factor of 2 compared to typical ISM values similar to what has previously been inferred for glycolaldehyde. The results point to the importance of ice surface chemistry for the formation of these complex organic molecules at different stages in the evolution of embedded protostars and demonstrate the use of accurate isotope measurements for understanding the history of individual species.

/pdf/the-alma-pils-survey-isotopic-composition-of-oxygen-342htoqnfa.pdf

The ALMA-PILS survey: isotopic composition of oxygen-containing complex organic molecules toward IRAS 16293-2422B

Context. Laboratory measurements and analysis of the microwave and millimeter-wave spectra of potential interstellar molecules are a prerequisite for their subsequent identification by radioastronomical techniques. The spectral analysis provides spectroscopic parameters that are used in the assignment procedure of the laboratory spectra, and that also predict the frequencies of transitions not measured in the laboratory with a high degree of precision. Aims. An experimental laboratory study and its theoretical analysis is presented for 13 C2-methyl formate (HCOO 13 CH3) allowing a search for this isotopologue in the Orion molecular cloud. The 13 C1-methyl formate (H 13 COOCH3) molecule was also searched for in this interstellar cloud, using previously published spectroscopic data. Methods. The experimental spectra of 13 C2-methyl formate were recorded in the microwave and sub-mm energy ranges (4–20 GHz, 8–80 GHz, 150–700 GHz). The spectra were analyzed using the Rho-Axis Method (RAM), which takes the CH3 internal rotation and the coupling between internal rotation and global rotation into account. Results. Twenty-seven spectroscopic constants of 13 C2-methyl formate have been obtained from a fit of 936 transitions of the ground torsional state with a standard (unitless) deviation of 1.08. A prediction of line positions and intensities is also produced. This prediction allowed us to identify 230 13 C2-methyl formate lines in the Orion interstellar molecular cloud. We refitted all previously published ground state transitions of the 13 C1-methyl formate molecule in order to provide a prediction of its ground state spectrum. 234 lines of 13 C1-methyl formate were detected in the Orion interstellar cloud using that prediction.

https://www.aanda.org/articles/aa/pdf/2009/24/aa11456-08.pdf

Rotational spectrum of 13 C 2 -methyl formate (HCOO 13 CH 3 ) and detection of the two 13 C-methyl formate in Orion

New centimeter-wave (7-80 GHz) and submillimeter-wave (580-661 GHz) spectra of a deuterated species of methyl formate (DCOOCH3) have been measured. Transitions with a maximum value of J = 64 and K = 36 have been assigned and fitted together with previous measurements. The internal rotation of this compound was treated using the so-called rho axis method. A total of 1703 transitions were fitted using this method. Only 24 parameters were employed in the final fit, which has an rms deviation of 94.2 kHz. The dipole moment and the nuclear quadrupole coupling constants of the deuterated specie have also been obtained. This new study has permitted a tentative detection of DCOOCH3 in Orion with the IRAM 30 m telescope based on the observation of more than 100 spectral features with low blending effects among the 400 lines expected in the observed frequency domain (for which over 300 are heavily blended with other species). These 100 transitions are above noise and confusion limited without heavy blending and cannot be assigned to any other species. Moreover, none of the strongest unblended transitions is missing. The derived source-averaged total column density for DCOOCH3 is 7.8 × 1014 cm–2 and the DCOOCH3/HCOOCH3 column density ratio varies between 0.02 and 0.06 in the different cloud components of Orion. This value is consistent with the deuteration enhancement found for other species in this cloud.

/pdf/rotational-spectrum-and-tentative-detection-of-dcooch3-4ku1wsvwh1.pdf

Rotational Spectrum and Tentative Detection of DCOOCH3-Methyl Formate in Orion

Context. Astronomical survey of interstellar molecular clouds needs a previous analysis of the spectra in the microwave and sub-mm energy range to be able to identify them. We obtained very accurate spectroscopic constants in a comprehensive laboratory analysis of rotational spectra. These constants can be used to predict transition frequencies that were not measured in the laboratory very precisely. Aims: We present an experimental study and a theoretical analysis of two 18O-methyl formate isotopologues, which were subsequently detected for the first time in Orion KL. Methods: The experimental spectra of both methyl formate isotopologues recorded in the microwave and sub-mm range from 1 to 660 GHz. Both spectra were analysed by using the rho-axis method (RAM) which takes into account the CH3 internal rotation. Results: We obtained spectroscopic constants of both 18O- methyl formate with high accuracy. Thousands of transitions were assigned and others predicted, which allowed us to detect both species in the IRAM 30 m line survey of Orion KL. Full Tables A.1 et A.2 are available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/538/A119

/pdf/microwave-and-submillimeter-spectroscopy-and-first-ism-3vis17cz4d.pdf

R. Janečkovà

Papers

The microwave spectrum of the mono deuterated species of methyl formate HCOOCH2D