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Register a new userThermal desorption of astrophysical relevant ice mixtures of acetaldehyde and acetonitrile from olivine dust
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Maria Angela Corazzi
Publication date
2021
fields
Physics
and research's language is
English
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Millimeter and centimeter observations are discovering an increasing number of interstellar complex organic molecules (iCOMs) in a large variety of star forming sites, from the earliest stages of star formation to protoplanetary disks and in comets. In this context it is pivotal to understand how the solid phase interactions between iCOMs and grain surfaces influence the thermal desorption process and, therefore, the presence of molecular species in the gas phase. In laboratory, it is possible to simulate the thermal desorption process deriving important parameters such as the desorption temperatures and energies. We report new laboratory results on temperature-programmed desorption (TPD) from olivine dust of astrophysical relevant ice mixtures of water, acetonitrile, and acetaldehyde. We found that in the presence of grains, only a fraction of acetaldehyde and acetonitrile desorbs at about 100 K and 120 K respectively, while 40% of the molecules are retained by fluffy grains of the order of 100 {mu}m up to temperatures of 190-210 K. In contrast with the typical assumption that all molecules are desorbed in regions with temperatures higher than 100 K, this result implies that about 40% of the molecules can survive on the grains enabling the delivery of volatiles towards regions with temperatures as high as 200 K and shifting inwards the position of the snowlines in protoplanetary disks. These studies offer a necessary support to interpret observational data and may help our understanding of iCOMs formation providing an estimate of the fraction of molecules released at various temperatures.
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We report an investigation of X-ray induced desorption of neutrals, cations and anions from CO ice. The desorption of neutral CO, by far the most abundant, is quantified and discussed within the context of its application to astrochemistry. The desorption of many different cations, including large cations up to the mass limit of the spectrometer, are observed. In contrast, the only desorbing anions detected are O$^-$ and C$^-$. The desorption mechanisms of all these species are discussed with the aid of their photodesorption spectrum. The evolution of the X-ray absorption spectrum shows significant chemical modifications of the ice upon irradiation, which along with the desorption of large cations gives a new insight into X-ray induced photochemistry in CO ice.
We present temperature programmed desorption (TPD) measurements of CO, CH$_4$, O$_2$ and CO$_2$ from the forsterite(010) surface in the sub-monolayer and multilayer coverage regimes. In the case of CO, CH$_4$ and O$_2$, multilayer growth begins prior to saturation of the monolayer peak, resulting in two clearly distinguishable desorption peaks. On the other hand a single peak for CO$_2$ is observed which shifts from high temperature at low coverage to low temperature at high coverages, sharpening upon multilayer formation. The leading edges are aligned for all the molecules in the multilayer coverage regime indicating zero order desorption. We have extracted multilayer desorption energies for these molecules using an Arrhenius analysis. For sub-monolayer coverages, we observe an extended desorption tail to higher temperature. Inversion analysis has been used to extract the coverage dependent desorption energies in the sub-monolayer coverage regime, from which we obtain the desorption energy distribution. We found that owing to the presence of multiple adsorption energy sites on the crystalline surface the typical desorption energies of these small molecules are significantly larger than obtained in previous measurements for several other substrates. Therefore molecules bound to crystalline silicate surfaces may remain locked in the solid state for a longer period of time before desorption into the gas phase.
Context. Infrared spectroscopy of star and planet forming regions is at the dawn of a new age with the upcoming James Webb Space Telescope. In support of these observations, laboratory spectra are required to identify complex organic molecules in the ices that cover the dust grains in these regions. Aims. This study aims to provide reference spectra to firmly detect icy methyl formate in the different stages of star and planet forming regions. Methyl formate is mixed in astronomically relevant matrices, and the peak positions, FWHMs, and relative band intensities are characterized for different temperatures to provide an analytical tool for astronomers. Methods. Methyl formate is deposited at 15 K under high-vacuum conditions. Specifically, methyl formate is deposited pure and mixed with CO, H$_2$CO, CH$_3$OH, H$_2$O, and CO:H$_2$CO:CH$_3$OH combined. Throughout the experiment infrared spectra are acquired with a FTIR spectrometer in the range from 4000-500 cm$^{-1}$ (2.5-20 $mu$m) at a spectral resolution of 0.5 cm$^{-1}$. Results. We present the characterization of five solid-state methyl formate vibrational modes in pure and astronomically relevant ice matrices. The five selected vibrational modes, namely the C=O stretch, C$-$O stretch, CH$_3$ rocking, O$-$CH$_3$ stretching, and OCO deformation, are best suited for a JWST identification of methyl formate. For each of these vibrational modes, and each of the mixtures the TvS heatmaps, peak position versus FWHM, and relative band intensities are given. Additionally, the acquired reference spectra of methyl formate are compared with Spitzer observations of HH 46. A tentative detection of methyl formate provides an upper limit to the column density of $1.7times10^{17}$ cm$^{-2}$, corresponding to an upper limit relative to water of $leq 2.2%$ and $leq 40%$ with respect to methanol.
Aims. Formamide (HCONH2) is the simplest molecule containing the peptide bond first detected in the gas phase in Orion-KL and SgrB2. In recent years, it has been observed in high temperature regions such as hot corinos, where thermal desorption is responsible for the sublimation of frozen mantles into the gas phase. The interpretation of observations can benefit from information gathered in the laboratory, where it is possible to simulate the thermal desorption process and to study formamide under simulated space conditions such as UV irradiation. Methods. Here, two laboratory analyses are reported: we studied formamide photo-stability under UV irradiation when it is adsorbed by space relevant minerals at 63 K and in the vacuum regime. We also investigated temperature programmed desorption of pure formamide ice in the presence of TiO2 dust before and after UV irradiation. Results. Through these analyses, the effects of UV degradation and the interaction between formamide and different minerals are compared.We find that silicates, both hydrates and anhydrates, offer molecules a higher level of protection from UV degradation than mineral oxides. The desorption temperature found for pure formamide is 220 K. The desorption temperature increases to 250 K when the formamide desorbs from the surface of TiO2 grains. Conclusions. Through the experiments outlined here, it is possible to follow the desorption of formamide and its fragments, simulate the desorption process in star forming regions and hot corinos, and constrain parameters such as the thermal desorption temperature of formamide and its fragments and the binding energies involved. Our results offer support to observational data and improve our understanding of the role of the grain surface in enriching the chemistry in space.
Sulfur is an abundant element in the cosmos and it is thus an important contributor to astrochemistry in the interstellar medium and in the Solar System. Astronomical observations of the gas and of the solid phases in the dense interstellar/circumstellar regions have evidenced that sulfur is underabundant. The hypothesis to explain such a circumstance is that it is incorporated in some species in the solid phase (i.e. as frozen gases and/or refractory solids) and/or in the gas phase, which for different reasons have not been observed so far. Here we wish to give a contribution to the field by studying the chemistry induced by thermal and energetic processing of frozen mixtures of sulfur dioxide (one of the most abundant sulfur-bearing molecules observed so far) and water. We present the results of a series of laboratory experiments concerning thermal processing of different H2O:SO2 mixtures and ion bombardment 30 keV He$^+$ of the same mixtures. We used in situ FTIR spectroscopy to investigate the induced effects. The results indicate that ionic species such as HSO$_{3}^{-}$, HSO$_{4}^{-}$, and S$_2$O$_{5}^{2-}$ are easily produced. Energetic processing also produces SO$_3$ polymers and a sulfurous refractory residue. The produced ionic species exhibit spectral features in a region that, in astronomical spectra of dense molecular clouds, is dominated by strong silicate absorption. However, such a dominant feature is associated with some spectral features, some of which have not yet been identified. We suggest adding the sulfur-bearing ionic species to the list of candidates to help explain some of those features.
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