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Register a new userA Systematic Study on the Absorption Features of Interstellar Ices in Presence of Impurities
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Spectroscopic studies play a key role in the identification and analysis of interstellar ices and their structure. Some molecules have been identified within the interstellar ices either as pure, mixed, or even as layered structures. Absorption band features of water ice can significantly change with the presence of different types of impurities (CO, CO2, CH3OH, H2CO, etc.). In this work, we carried out a theoretical investigation to understand the behavior of water band frequency, and strength in the presence of impurities. The computational study has been supported and complemented by some infrared spectroscopy experiments aimed at verifying the effect of HCOOH, NH3 , and CH3 OH on the band profiles of pure H2O ice. Specifically, we explored the effect on the band strength of libration, bending, bulk stretching, and free-OH stretching modes. Computed band strength profiles have been compared with our new and existing experimental results, thus pointing out that vibrational modes of H2O and their intensities can change considerably in the presence of impurities at different concentrations. In most cases, the bulk stretching mode is the most affected vibration, while the bending is the least affected mode. HCOOH was found to have a strong influence on the libration, bending, and bulk stretching band profiles. In the case of NH3, the free-OH stretching band disappears when the impurity concentration becomes 50%. This work will ultimately aid a correct interpretation of future detailed spaceborne observations of interstellar ices by means of the upcoming JWST mission.
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Heavily obscured active galactic nuclei (AGNs) are known to show deep silicate absorption features in the mid-infrared (IR) wavelength range of 10--20~$mu$m. The detailed profiles of the features reflect the properties of silicate dust, which are likely to include information on AGN activities obscured by large amounts of dust. In order to reveal AGN activities obscured by large amounts of dust, we select 115 mid-IR spectra of heavily obscured AGNs observed by Spitzer/IRS, and systematically analyze the composition of silicate dust by spectral fitting using the 10~$mu$m amorphous and 23~$mu$m crystalline bands. We find that the main component of the silicate dust obscuring AGNs is amorphous olivine, the median mass column density of which is one order of magnitude higher than those of the minor components of amorphous pyroxene and crystalline forsterite. The median mass fraction of the amorphous pyroxene, $sim$2%, is significantly lower than that of the diffuse interstellar medium (ISM) dust in our Galaxy, while the median mass fraction of the crystalline forsterite, $sim$6%, is higher than that of the diffuse ISM dust. We also find that the mass fractions of the amorphous pyroxene and the crystalline forsterite positively correlate with each other. The low mass fraction of the amorphous pyroxene suggests that the obscuring silicate dust is newly formed, originating from starburst activities. The relatively high mass fraction of crystalline forsterite implies that the silicate dust is processed in the high temperature environment close to the nucleus and transported to outer cooler regions by molecular outflows. The positive correlation between the mass fractions can be naturally explained considering that amorphous pyroxene is transformed from crystalline forsterite by ion bombardments.
In this work, we reexamine sulfur chemistry occurring on and in the ice mantles of interstellar dust grains, and report the effects of two new modifications to standard astrochemical models; namely, (a) the incorporation of cosmic ray-driven radiation chemistry and (b) the assumption of fast, non-diffusive reactions for key radicals in the bulk. Results from our models of dense molecular clouds show that these changes can have a profound influence on the abundances of sulfur-bearing species in ice mantles, including a reduction in the abundance of solid-phase H$_2$S and HS, and a significant increase in the abundances of OCS, SO$_2$, as well as pure allotropes of sulfur, especially S$_8$. These pure-sulfur species - though nearly impossible to observe directly - have long been speculated to be potential sulfur reservoirs and our results represent possibly the most accurate estimates yet of their abundances in the dense ISM. Moreover, the results of these updated models are found to be in good agreement with available observational data. Finally, we examine the implications of our findings with regard to the as-yet-unknown sulfur reservoir thought to exist in dense interstellar environments.
We present a model for the formation of large organic molecules in dark clouds. The molecules are produced in the high density gas-phase that exists immediately after ice mantles are explosively sublimated. The explosions are initiated by the catastrophic recombination of trapped atomic hydrogen. We propose that, in molecular clouds, the processes of freeze-out onto ice mantles, accumulation of radicals, explosion and then rapid (three-body) gas-phase chemistry occurs in a cyclic fashion. This can lead to a cumulative molecular enrichment of the interstellar medium. A model of the time-dependent chemistries, based on this hypothesis, shows that significant abundances of large molecular species can be formed, although the complexity of the species is limited by the short expansion timescale in the gas, immediately following mantle explosion. We find that this mechanism may be an important source of smaller organic species, such as methanol and formaldehyde, as well as precursors to bio-molecule formation. Most significantly, we predict the gas-phase presence of these larger molecular species in quiescent molecular clouds and not just dynamically active regions, such as hot cores. As such the mechanism that we propose complements alternative methods of large molecule formation, such as those that invoke solid-state chemistry within activated ice mantles.
Isolated dense molecular cores are investigated to study the onset of complex organic molecule formation in interstellar ice. Sampling three cores with ongoing formation of low-mass stars (B59, B335, and L483) and one starless core (L694-2) we sample lines of sight to nine background stars and five young stellar objects (YSOs; A_K ~0.5 - 4.7). Spectra of these stars from 2-5 $mu$m with NASAs Infrared Telescope Facility (IRTF) simultaneously display signatures from the cores of H$_2$O (3.0 $mu$m), CH$_3$OH (C-H stretching mode, 3.53 $mu$m) and CO (4.67 $mu$m) ices. The CO ice is traced by nine stars in which five show a long wavelength wing due to a mixture of CO with polar ice (CO$_r$), presumably CH$_3$OH. Two of these sight lines also show independent detections of CH$_3$OH. For these we find the ratio of the CH$_3$OH:CO$_r$ is 0.55$pm$0.06 and 0.73$pm$0.07 from L483 and L694-2, respectively. The detections of both CO and CH$_3$OH for the first time through lines of sight toward background stars observationally constrains the conversion of CO into CH$_3$OH ice. Along the lines of sight most of the CO exists in the gas phase and $leq$15% of the CO is frozen out. However, CH$_3$OH ice is abundant with respect to CO (~50%) and exists mainly as a CH$_3$OH-rich CO ice layer. Only a small fraction of the lines of sight contains CH$_3$OH ice, presumably that with the highest density. The high conversion of CO to CH$_3$OH can explain the abundances of CH$_3$OH ice found in later stage Class 1 low mass YSO envelopes (CH$_3$OH:CO$_r$ ~ 0.5-0.6). For high mass YSOs and one Class 0 YSO this ratio varies significantly implying local variations can affect the ice formation. The large CH$_3$OH ice abundance indicates that the formation of complex organic molecules is likely during the pre-stellar phase in cold environments without higher energy particle interactions (e.g. cosmic rays).
Context. Methane is among the main components of the ice mantles of insterstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims. This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investigated. By studying the methane desorption from layered CH4:CO ice, indirect desorption processes triggered by the excitation of the CO molecules is monitored and quantified. Methods. Tunable monochromatic VUV light from the DESIRS beamline of the SOLEIL synchrotron is used in the 7 - 13.6 eV (177 - 91 nm) range to irradiate pure CH4 or layers of CH4 deposited on top of CO ice samples. The release of species in the gas phase is monitored by quadrupole mass spectrometry and absolute photodesorption yields of intact CH4 are deduced. Results. CH4 photodesorbs for photon energies higher than ~9.1 eV (~136 nm). The photodesorption spectrum follows the absorption spectrum of CH4, which confirms a desorption mechanism mediated by electronic transitions in the ice. When it is deposited on top of CO, CH4 desorbs between 8 and 9 eV with a pattern characteristic of CO absorption, indicating desorption induced by energy transfer from CO molecules. Conclusions. The photodesorption of CH4 from the pure ice in various interstellar environments is around 2.0 x 10^-3 molecules per incident photon. Results on CO-induced indirect desorption of CH4 provide useful insights for the generalization of this process to other molecules co-existing with CO in ice mantles.
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