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Millimeter-wave spectroscopy of the $^{13}$CH$_3$OD isotopic species of methyl alcohol

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 Added by Holger M\\\"uller
 Publication date 2021
  fields Physics
and research's language is English




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The dramatic increase in sensitivity, spectral coverage and resolution of radio astronomical facilities in recent years has opened new possibilities for observation of chemical differentiation and isotopic fractionation in protostellar sources to shed light on their spatial and temporal evolution. In warm interstellar environments, methanol is an abundant species, hence spectral data for its isotopic forms are of special interest. In the present work, the millimeter-wave spectrum of the $^{13}$CH$_3$OD isotopologue has been investigated over the region from 150$-$510 GHz to provide a set of transition frequencies for potential astronomical application. The focus is on two types of prominent $^{13}$CH$_3$OD spectral groupings, namely the $a$-type $^qR$-branch multiplets and the $b$-type $Q$-branches. Line positions are reported for the $^qR(J)$ clusters for $J = 3$ to 10 for the $v_{rm t} = 0$ and 1 torsional states, and for a number of $v_{rm t} = 0$ and 1 $^rQ(J)$ or $^pQ(J)$ line series up to $J = 25$. The frequencies have been fitted to a multi-parameter torsion-rotation Hamiltonian, and upper level excitation energies have been calculated from the resulting molecular constants.



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Methyl mercaptan (CH$_3$SH) is an important sulfur-bearing species in the interstellar medium, terrestrial environment, and potentially in planetary atmospheres. The aim of the present study is to provide accurate spectroscopic parameters for the most abundant minor isotopolog CH$_3$$^{34}$SH to support radio astronomical observations at millimeter and submillimeter wavelengths. The rotational spectrum of CH$_3$$^{34}$SH, which is complicated by the large-amplitude internal rotation of the CH$_3$ group versus the $^{34}$SH frame, was investigated in the 49$-$510 GHz and 1.1$-$1.5 THz frequency ranges in natural isotopic abundance. The analysis of the spectrum was performed up to the second excited torsional state, and the obtained data were modeled with the RAM36 program. A fit within experimental accuracy was obtained with a RAM Hamiltonian model that uses 72 parameters. Predictions based on this fit are used to search for CH$_3$$^{34}$SH with the Atacama Large Millimeter/submillimeter Array (ALMA) toward the hot molecular core Sgr B2(N2), but blends with emission lines of other species prevent its firm identification in this source.
Methyl mercaptan (CH3SH) is a known interstellar molecule with abundances high enough that the detection of some of its minor isotopologues is promising. The present study aims at providing accurate spectroscopic parameters for the (13)CH3SH isotopologue to facilitate its identification in the interstellar medium at millimetre and submillimetre wavelengths. Through careful analysis of recent CH3SH spectra from 49-510 GHz and 1.1-1.5 THz recorded at natural isotopic composition, extensive assignments were possible not only for the ground torsional state of (13)CH3SH, but also in the first and second excited states. The torsion-rotation spectrum displays complex structure due to the large-amplitude internal rotation of the (13)CH3 group, similar to the main and other minor isotopic species of methyl mercaptan. The assigned transition frequencies have been fitted to within experimental error with a 52-parameter model employing the RAM36 programme. With predictions based on this fit, (13)CH3SH was searched for in spectra from the Atacama Large Millimetre/submillimetre Array (ALMA) towards the Galactic centre source Sgr B2(N2). Several transitions were expected to be observable, but all of them turned out to be severely blended with emission from other species, which prevents us from identifying (13)CH3SH in this source.
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The rotational spectral lines of c-C$_3$H$_2$ and two kinds of the $^{13}$C isotopic species, c-$^{13}$CCCH$_2$ ($C_{2v}$ symmetry) and c-CC$^{13}$CH$_2$ ($C_s$ symmetry) have been observed in the 1-3 mm band toward the low-mass star-forming region L1527. We have detected 7, 3, and 6 lines of c-C$_3$H$_2$, c-$^{13}$CCCH$_2$ , and c-CC$^{13}$CH$_2$, respectively, with the Nobeyama 45 m telescope, and 34, 6, and 13 lines, respectively, with the IRAM 30 m telescope, where 7, 2, and 2 transitions, respectively, are observed with the both telescopes. With these data, we have evaluated the column densities of the normal and $^{13}$C isotopic species. The [c-C$_3$H$_2$]/[c-$^{13}$CCCH$_2$] ratio is determined to be $310pm80$, while the [c-C$_3$H$_2$]/[c-CC$^{13}$CH$_2$] ratio is determined to be $61pm11$. The [c-C$_3$H$_2$]/[c-$^{13}$CCCH$_2$] and [c-C$_3$H$_2$]/[c-CC$^{13}$CH$_2$] ratios expected from the elemental $^{12}$C/$^{13}$C ratio are 60-70 and 30-35, respectively, where the latter takes into account the statistical factor of 2 for the two equivalent carbon atoms in c-C$_3$H$_2$. Hence, this observation further confirms the dilution of the $^{13}$C species in carbon-chain molecules and their related molecules, which are thought to originate from the dilution of $^{13}$C$^+$ in the gas-phase C$^+$ due to the isotope exchange reaction: $mathrm{^{13}C^++COrightarrow{}^{13}CO+C^+}$. Moreover, the abundances of the two $^{13}$C isotopic species are different from each other. The ratio of c-$mathrm{^{13}CCCH_2}$ species relative to c-$mathrm{CC^{13}CH_2}$ is determined to be $0.20pm0.05$. If $^{13}$C were randomly substituted for the three carbon atoms, the [c-$mathrm{^{13}CCCH_2}$]/[c-$mathrm{CC^{13}CH_2}$] ratio would be 0.5. Hence, the observed ratio indicates that c-$mathrm{CC^{13}CH_2}$ exists more favorably. Possible origins of the different abundances are discussed.
89 - G. Langston , B. Turner 2006
The $^{13}C$ substitutions of molecule $HC_7N$ were observed in TMC-1 using the J = 12 - 11, J = 13 - 12 rotational transitions in the frequency range 12.4 to 13.6 GHz. We present the first detection the $^{13}C$ isotopic species of $HC_7N$ in the interstellar medium, based on the average of a number of weak rotational transitions. This paper describes the calibration and data averaging process that is also used in a search for large cyanopolyyne molecules in TMC-1 using the 100m Robert C. Byrd Green Bank Telescope (GBT). The capabilities of the GBT 11 to 15 GHz observing system are described along with a discussion of numerical methods for averaging observations of a number of weak spectral lines to detect new interstellar molecules.
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