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Register a new userFormation of interstellar SH$^+$ from vibrationally excited H$_2$: Quantum study of S$^+$ + H$_2$ $rightleftarrows$ SH$^+$ + H reactions and inelastic collisions
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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 developed 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.
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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+0.693-0.027. 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$SH are discussed, as well as the relevance of these compounds in the synthesis of prebiotic proteins in the primitive Earth.
We have extended the pure rotational investigation of the two isomers syn and anti vinyl mercaptan to the millimeter domain using a frequency-multiplication spectrometer. The species were produced by a radiofrequency discharge in 1,2-ethanedithiol. Additional transitions have been re-measured in the centimeter band using Fourier-transform microwave spectroscopy to better determine rest frequencies of transitions with low-$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.
SH$^+$ is a surprisingly widespread molecular ion in diffuse interstellar clouds. There, it plays an important role triggering the sulfur chemistry. In addition, SH$^+$ emission lines have been detected at the UV-illuminated edges of dense molecular clouds, mbox{so-called} photo-dissociation regions (PDRs), and toward high-mass protostars. An accurate determination of the SH$^+$ abundance and of the physical conditions prevailing in these energetic environments relies on knowing the rate coefficients of inelastic collisions between SH$^+$ molecules and hydrogen atoms, hydrogen molecules, and electrons. In this paper, we derive SH$^+$--H fine and hyperfine-resolved rate coefficients from the recent quantum calculations for the SH$^+$--H collisions, including inelastic, exchange and reactive processes. The method used is based on the infinite order sudden approach. State-to-state rate coefficients between the first 31 fine levels and 61 hyperfine levels of SH$^+$ were obtained for temperatures ranging from 10 to 1000 K. Fine structure-resolved rate coefficients present a strong propensity rule in favour of $Delta j = Delta N$ transitions. The $Delta j = Delta F$ propensity rule is observed for the hyperfine transitions. {The new rate coefficients will help significantly in the interpretation of SH$^+$ spectra from PDRs and UV-irradiated shocks where the abundance of hydrogen atoms with respect to hydrogen molecules can be significant.
We present a model in which the 22 GHz H$_2$O masers observed in star-forming regions occur behind shocks propagating in dense regions (preshock density $n_0 sim 10^6 - 10^8$ cm$^{-3}$). We focus on high-velocity ($v_s > 30$ km s$^{-1}$) dissociative J shocks in which the heat of H$_2$ re-formation maintains a large column of $sim 300-400$ K gas; at these temperatures the chemistry drives a considerable fraction of the oxygen not in CO to form H$_2$O. The H$_2$O column densities, the hydrogen densities, and the warm temperatures produced by these shocks are sufficiently high to enable powerful maser action. The observed brightness temperatures (generally $sim 10^{11} - 10^{14}$ K) are the result of coherent velocity regions that have dimensions in the shock plane that are 10 to 100 times the shock thickness of $sim 10^{13}$ cm. The masers are therefore beamed towards the observer, who typically views the shock edge-on, or perpendicular to the shock velocity; the brightest masers are then observed with the lowest line of sight velocities with respect to the ambient gas. We present numerical and analytic studies of the dependence of the maser inversion, the resultant brightness temperature, the maser spot size and shape, the isotropic luminosity, and the maser region magnetic field on the shock parameters and the coherence path length; the overall result is that in galactic H$_2$O 22 GHz masers these observed parameters can be produced in J shocks with $n_0sim 10^6 - 10^8$ cm$^{-3}$ and $v_s sim 30 -200$ km s$^{-1}$. A number of key observables such as maser shape, brightness temperature, and global isotropic luminosity depend only on the particle flux into the shock, $j=n_0v_s$, rather than on $n_0$ and $v_s$ separately.
Rotational spectra in four new excited vibrational levels of the linear carbon chain radical C$_4$H radical were observed in the millimeter band between 69 and 364 GHz in a low pressure glow discharge, and two of these were observed in a supersonic molecular beam between 19 and 38 GHz. All have rotational constants within 0.4% of the $^2Sigma^+$ ground vibrational state of C$_4$H and were assigned to new bending vibrational levels, two each with $^2Sigma$ and $^2Pi$ vibrational symmetry. The new levels are tentatively assigned to the $1 u_6$ and $1 u_5$ bending vibrational modes (both with $^2Pi$ symmetry), and the $1 u_6 + 1 u_7$ and $1 u_5 + 1 u_6$ combination levels ($^2Sigma$ symmetry) on the basis of the derived spectroscopic constants, relative intensities in our discharge source, and published laser spectroscopic and quantum calculations. Prior spectroscopic constants in the $1 u_7$ and $2 u_7$ levels were refined. Also presented are interferometric maps of the ground state and the $1 u_7$ level obtained with the SMA near 257 GHz which show that C$_4$H is present near the central star in IRC+10216. We found no evidence with the SMA for the new vibrationally excited levels of C$_4$H at a peak flux density averaged over a $3^{primeprime}$ synthesized beam of $ge 0.15$ Jy/beam in the 294-296 and 304-306 GHz range, but it is anticipated that rotational lines in the new levels might be observed in IRC+10216 when ALMA attains its full design capability.
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