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تسجيل مستخدم جديدBottlenecks to interstellar sulfur chemistry: Sulfur-bearing hydrides in UV-illuminated gas and grains
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Hydride molecules lie at the base of interstellar chemistry, but the synthesis of sulfuretted hydrides is poorly understood. Motivated by new observations of the Orion Bar PDR - 1 resolution ALMA images of SH+; IRAM 30m detections of H2S, H2S34, and H2S33; H3S+ (upper limits); and SOFIA observations of SH - we perform a systematic study of the chemistry of S-bearing hydrides. We determine their column densities using coupled excitation, radiative transfer as well as chemical formation and destruction models. We revise some of the key gas-phase reactions that lead to their chemical synthesis. This includes ab initio quantum calculations of the vibrational-state-dependent reactions SH+ + H2 <-> H2S+ + H and S + H2 <-> SH + H. We find that reactions of UV-pumped H2 (v>1) with S+ explain the presence of SH+ in a high thermal-pressure gas component, P_th~10^8 cm^-3 K, close to the H2 dissociation front. However, subsequent hydrogen abstraction reactions of SH+, H2S+, and S with vibrationally excited H2, fail to ultimately explain the observed H2S column density (~2.5x10^14 cm^-2, with an ortho-to-para ratio of 2.9+/-0.3). To overcome these bottlenecks, we build PDR models that include a simple network of grain surface reactions leading to the formation of solid H2S (s-H2S). The higher adsorption binding energies of S and SH suggested by recent studies imply that S atoms adsorb on grains (and form s-H2S) at warmer dust temperatures and closer to the UV-illuminated edges of molecular clouds. Photodesorption and, to a lesser extent, chemical desorption, produce roughly the same H2S column density (a few 10^14 cm-^2) and abundance peak (a few 10^-8) nearly independently of n_H and G_0. This agrees with the observed H2S column density in the Orion Bar as well as at the edges of dark clouds without invoking substantial depletion of elemental sulfur abundances.
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We present an observational study of the sulfur (S)-bearing species towards Orion KL at 1.3 mm by combining ALMA and IRAM-30,m single-dish data. At a linear resolution of $sim$800 au and a velocity resolution of 1 $mathrm{km, s^{-1}, }$, we have iden
tified 79 molecular lines from 6 S-bearing species. In these S-bearing species, we found a clear dichotomy between carbon-sulfur compounds and carbon-free S-bearing species in various characteristics, e.g., line profiles, spatial morphology, and molecular abundances with respect to $rm H_2$. Lines from the carbon-sulfur compounds (i.e., OCS, $^{13}$CS, H$_2$CS) exhibit spatial distributions concentrated around the continuum peaks and extended to the south ridge. The full width at half maximum (FWHM) linewidth of these molecular lines is in the range of 2 $sim$ 11 $mathrm{km, s^{-1}, }$. The molecular abundances of OCS and H$_2$CS decrease slightly from the cold ($sim$68 K) to the hot ($sim$176 K) regions. In contrast, lines from the carbon-free S-bearing species (i.e., SO$_2$, $^{34}$SO, H$_2$S) are spatially more extended to the northeast of mm4, exhibiting broader FWHM linewidths (15 $sim$ 26 $mathrm{km, s^{-1}, }$). The molecular abundances of carbon-free S-bearing species increase by over an order of magnitude as the temperature increase from 50 K to 100 K. In particular, $mathrm{^{34}SO/^{34}SO_2}$ and $mathrm{OCS/SO_2}$ are enhanced from the warmer regions ($>$100 K) to the colder regions ($sim$50 K). Such enhancements are consistent with the transformation of SO$_2$ at warmer regions and the influence of shocks.
The elemental depletion of interstellar sulfur from the gas phase has been a recurring challenge for astrochemical models. Observations show that sulfur remains relatively non-depleted with respect to its cosmic value throughout the diffuse and trans
lucent stages of an interstellar molecular cloud, but its gas-phase constituents cannot account for this cosmic value towards higher-density environments. We have attempted to address this issue by modeling the evolution of an interstellar cloud from its pristine state as a diffuse atomic cloud to a molecular environment of much higher density, using a gas/grain astrochem. code and an enhanced sulfur reaction network. A common gas/grain reaction network has been systematically updated and greatly extended based on previous lit. and models, with a focus on the grain chemistry and processes. A simple model was used to benchmark the resulting network updates, and the results of the model were compared to typical astronomical observations sourced from the literature. Our new gas/grain model is able to reproduce the elemental depletion of sulfur, whereby sulfur can be depleted from the gas-phase by two orders of magnitude, and this process may occur under dark cloud conditions if the cloud has a chemical age of at least 1 Myrs. The resulting mix of sulfur-bearing species on the grain ranges across all the most common chemical elements (H/C/N/O), not dissimilar to the molecules observed in cometary environments. Notably, this mixture is not dominated simply by H2S, unlike all other current astrochem. models. Despite our relatively simple physical model, most of the known gas-phase S-bearing molecular abundances are accurately reproduced under dense conditions, however they are not expected to be the primary molecular sinks of sulfur. Our model predicts that most of the missing sulfur is in the form of organo-sulfur species trapped on grains.
Context. Several sulfur-bearing molecules are observed in the interstellar medium and in comets, in strong contrast to protoplanetary disks where only CS, H$_2$CS and SO have been detected so far. Aims. We combine observations and chemical models to
constrain the sulfur abundances and their sensitivity to physical and chemical conditions in the DM Tau protoplanetary disk. Methods. We obtained $0.5^{}$ ALMA observations of DM Tau in Bands 4 and 6 in lines of CS, SO, SO$_2$, OCS, CCS, H$_2$CS and H$_2$S, achieving a $sim 5$ mJy sensitivity. Using the non-LTE radiative transfer code RADEX and the forward-modeling tool DiskFit, disk-averaged CS column densities and upper limits for the other species were derived. Results. Only CS was detected with a derived column density of $sim 2-6 times 10^{12}$ cm$^{-2}$. We report a first tentative detection of SO$_2$ in DM Tau. The upper limits range between $sim 10^{11}$ and $10^{14}$ cm$^{-2}$ for the other S-bearing species. The best-fit chemical model matching these values requires a gas-phase C/O ratio of > 1 at $r sim 50-100$ au. With chemical modeling we demonstrate that sulfur-bearing species could be robust tracers of the gas-phase C/O ratio, surface reaction rates, grain size and UV intensities. Conclusions. The lack of detections of a variety of sulfur-bearing molecules in DM Tau other than CS implies a dearth of reactive sulfur in the gas phase, either through efficient freeze-out or because most of the elemental sulfur is in other large species, as found in comets. The inferred high CS/SO and CS/SO$_2$ ratios require a non-solar C/O gas-phase ratio of > 1, consistent with the recent observations of hydrocarbon rings in DM Tau. The stronger depletion of oxygen-bearing S-species compared to CS is likely linked to the low observed abundances of gaseous water in DM Tau and points to a removal mechanism of oxygen from the gas.
Barnard B1b has revealed as one of the most interesting globules from the chemical and dynamical point of view. It presents a rich molecular chemistry characterized by large abundances of deuterated and complex molecules. Furthermore, it hosts an ext
remely young Class 0 object and one candidate to First Hydrostatic Core (FHSC). Our aim was to determine the cosmic ray ionization rate and the depletion factors in this extremely young star forming region. We carried out a spectral survey towards Barnard 1b as part of the IRAM Large program ASAI using the IRAM 30-m telescope at Pico Veleta (Spain). This provided a very complete inventory of neutral and ionic C-, N- and S- bearing species with, up to our knowledge, the first secure detections of the deuterated ions DCS+ and DOCO+. We used a state-of-the-art pseudo-time-dependent gas-phase chemical model to determine the value of the cosmic ray ionization rate and the depletion factors. The observational data were well fitted with $zeta_{H_2}$ between 3E-17 s$^{-1}$ and 1E-16 s$^{-1}$. Elemental depletions were estimated to be ~10 for C and O, ~1 for N and ~25 for S. Barnard B1b presents similar depletions of C and O than those measured in pre-stellar cores. The depletion of sulfur is higher than that of C and O but not as extreme as in cold cores. In fact, it is similar to the values found in some bipolar outflows, hot cores and photon-dominated regions. Several scenarios are discussed to account for these peculiar abundances. We propose that it is the consequence of the initial conditions (important outflows and enhanced UV fields in the surroundings) and a rapid collapse (~0.1 Myr) that permits to maintain most S- and N-bearing species in gas phase to great optical depths. The interaction of the compact outflow associated with B1b-S with the surrounding material could enhance the abundances of S-bearing molecules, as well.
The recent discovery of superconductivity at 190~K in highly compressed H$_{2}$S is spectacular not only because it sets a record high critical temperature, but because it does so in a material that appears to be, and we argue here that it is, a conv
entional strong-coupling BCS superconductor. Intriguingly, superconductivity in the observed pressure and temperature range was predicted theoretically in a similar compound H$_{3}$S. Several important questions about this remarkable result, however, are left unanswered: (1) Does the stoichiometry of the superconducting compound differ from the nominal composition, and could it be the predicted H$_{3}$S compound? (2) Is the physical origin of the anomalously high critical temperature related only to the high H phonon frequencies, or does strong electron-ion coupling play a role? We show that at experimentally relevant pressures H$_2$S is unstable, decomposing into H$_3$S and S, and that H$_3$S has a record high $T_c$ due to its covalent bonds driven metallic. The main reason for this extraordinarily high $T_c$ in H$_3$S as compared with MgB$_2$, another compound with a similar superconductivity mechanism, is the high vibrational frequency of the much lighter H atoms.
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