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تسجيل مستخدم جديدSubmillimeter spectroscopy and astronomical searches of vinyl mercaptan, C$_2$H$_3$SH
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We have extended the pure rotational investigation of the two isomers syn and anti vinyl mercaptan to the millimeter domain using a frequency-multiplication spectrometer. The species were produced by a radiofrequency discharge in 1,2-ethanedithiol. Additional transitions have been re-measured in the centimeter band using Fourier-transform microwave spectroscopy to better determine rest frequencies of transitions with low-$J$ and low-$K_a$ values. Experimental investigations were supported by quantum chemical calculations on the energetics of both the [C$_2$,H$_4$,S] and [C$_2$,H$_4$,O] isomeric families. Interstellar searches for both syn and anti vinyl mercaptan as well as vinyl alcohol were performed in the EMoCA (Exploring Molecular Complexity with ALMA) spectral line survey carried out toward Sagittarius (Sgr) B2(N2) with the Atacama Large Millimeter/submillimeter Array (ALMA). Highly accurate experimental frequencies (to better than 100 kHz accuracy) for both syn and anti isomers of vinyl mercaptan have been measured up to 250 GHz; these deviate considerably from predictions based on extrapolation of previous microwave measurements. Reliable frequency predictions of the astronomically most interesting millimeter-wave lines for these two species can now be derived from the best-fit spectroscopic constants. From the energetic investigations, the four lowest singlet isomers of the [C$_2$,H$_4$,S] family are calculated to be nearly isoenergetic, which makes this family a fairly unique test bed for assessing possible reaction pathways. Upper limits for the column density of syn and anti vinyl mercaptan are derived toward the extremely molecule-rich star-forming region Sgr B2(N2) enabling comparison with selected complex organic molecules.
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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 mos
t 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.
The chemical compounds carrying the thiol group (-SH) have been considered essential in recent prebiotic studies regarding the polymerization of amino acids. We have searched for this kind of compounds toward the Galactic Centre quiescent cloud G+0.6
93-0.027. We report the first detection in the interstellar space of the trans-isomer of monothioformic acid (t-HC(O)SH) with an abundance of $sim,$1$,times,$10$^{-10}$. Additionally, we provide a solid confirmation of the gauche isomer of ethyl mercaptan (g-C$_2$H$_5$SH) with an abundance of $sim,$3$,times,$10$^{-10}$, and we also detect methyl mercaptan (CH$_3$SH) with an abundance of $sim,$5$,times,$10$^{-9}$. Abundance ratios were calculated for the three SH-bearing species and their OH-analogues, revealing similar trends between alcohols and thiols with increasing complexity. Possible chemical routes for the interstellar synthesis of t-HC(O)SH, CH$_3$SH and C$_2$H$_5$SH are discussed, as well as the relevance of these compounds in the synthesis of prebiotic proteins in the primitive Earth.
The rate constants for the formation, destruction, and collisional excitation of SH$^+$ are calculated from quantum mechanical approaches using two new SH$_2^+$ potential energy surfaces (PESs) of $^4A$ and $^2A$ electronic symmetry. The PESs were de
veloped to describe all adiabatic states correlating to the SH$^+$ ($^3Sigma^-$) + H($^2S$) channel. The formation of SH$^+$ through the S$^+$ + H$_2$ reaction is endothermic by $approx$ 9860 K, and requires at least two vibrational quanta on the H$_2$ molecule to yield significant reactivity. Quasi-classical calculations of the total formation rate constant for H$_2$($v=2$) are in very good agreement with the quantum results above 100K. Further quasi-classical calculations are then performed for $v=3$, 4, and 5 to cover all vibrationally excited H$_2$ levels significantly populated in dense photodissociation regions (PDR). The new calculated formation and destruction rate constants are two to six times larger than the previous ones and have been introduced in the Meudon PDR code to simulate the physical and illuminating conditions in the Orion bar prototypical PDR. New astrochemical models based on the new molecular data produce four times larger SH$^+$ column densities, in agreement with those inferred from recent ALMA observations of the Orion bar.
We report the first detection in space of the cumulene carbon chain $l$-H$_2$C$_5$. A total of eleven rotational transitions, with $J_{up}$ = 7-10 and $K_a$ = 0 and 1, were detected in TMC-1 in the 31.0-50.4 GHz range using the Yebes 40m radio telesc
ope. We derive a column density of (1.8$pm$0.5)$times$10$^{10}$ cm$^{-2}$. In addition, we report observations of other cumulene carbenes detected previously in TMC-1, to compare their abundances with the newly detected cumulene carbene chain. We find that $l$-H$_2$C$_5$ is $sim$4.0 times less abundant than the larger cumulene carbene $l$-H$_2$C$_6$, while it is $sim$300 and $sim$500 times less abundant than the shorter chains $l$-H$_2$C$_3$ and $l$-H$_2$C$_4$. We discuss the most likely gas-phase chemical routes to these cumulenes in TMC-1 and stress that chemical kinetics studies able to distinguish between different isomers are needed to shed light on the chemistry of C$_n$H$_2$ isomers with $n$,$>$,3.
A long standing problem in astrochemistry is the inability of many current models to account for missing sulfur content. Many relatively simple species that may be good candidates to sequester sulfur have not been measured experimentally at the high
spectral resolution necessary to enable radioastronomical identification. On the basis of new laboratory data, we report searches for the rotational lines in the microwave, millimeter, and sub-millimeter regions of the sulfur-containing hydrocarbon HCCSH. This simple species would appear to be a promising candidate for detection in space owing to the large dipole moment along its $b$-inertial axis, and because the bimolecular reaction between two highly abundant astronomical fragments (CCH and SH radicals) may be rapid. An inspection of multiple line surveys from the centimeter to the far-infrared toward a range of sources from dark clouds to high-mass star-forming regions, however, resulted in non-detections. An analogous search for the lowest-energy isomer, H$_2$CCS, is presented for comparison, and also resulted in non-detections. Typical upper limits on the abundance of both species relative to hydrogen are $10^{-9}$-$10^{-10}$. We thus conclude that neither isomer is a major reservoir of interstellar sulfur in the range of environments studied. Both species may still be viable candidates for detection in other environments or at higher frequencies, providing laboratory frequencies are available.
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