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Register a new userDesorption of CO and O2 interstellar ice analogs
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Solid O2 has been proposed as a possible reservoir for oxygen in dense clouds through freeze-out processes. The aim of this work is to characterize quantitatively the physical processes that are involved in the desorption kinetics of CO-O2 ices by interpreting laboratory temperature programmed desorption (TPD) data. This information is used to simulate the behavior of CO-O2 ices under astrophysical conditions. The TPD spectra have been recorded under ultra high vacuum conditions for pure, layered and mixed morphologies for different thicknesses, temperatures and mixing ratios. An empirical kinetic model is used to interpret the results and to provide input parameters for astrophysical models. Binding energies are determined for different ice morphologies. Independent of the ice morphology, the desorption of O2 is found to follow 0th-order kinetics. Binding energies and temperature-dependent sticking probabilities for CO-CO, O2-O2 and CO-O2 are determined. O2 is slightly less volatile than CO, with binding energies of 912+-15 versus 858+-15 K for pure ices. In mixed and layered ices, CO does not co-desorb with O2 but its binding energies are slightly increased compared with pure ice whereas those for O2 are slightly decreased. Lower limits to the sticking probabilities of CO and O2 are 0.9 and 0.85, respectively, at temperatures below 20K. The balance between accretion and desorption is studied for O2 and CO in astrophysically relevant scenarios. Only minor differences are found between the two species, i.e., both desorb between 16 and 18K in typical environments around young stars. Thus, clouds with significant abundances of gaseous CO are unlikely to have large amounts of solid O2.
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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.
The 4.62 micron absorption band, observed along the line-of-sight towards various young stellar objects, is generally used as a qualitative indicator for energetic processing of interstellar ice mantles. This interpretation is based on the excellent fit with OCN-, which is readily formed by ultraviolet (UV) or ion-irradiation of ices containing H2O, CO and NH3. However, the assignment requires both qualitative and quantitative agreement in terms of the efficiency of formation as well as the formation of additional products. Here, we present the first quantitative results on the efficiency of laboratory formation of OCN- from ices composed of different combinations of H2O, CO, CH3OH, HNCO and NH3 by UV- and thermally-mediated solid state chemistry. Our results show large implications for the use of the 4.62 micron feature as a diagnostic for energetic ice-processing. UV-mediated formation of OCN- from H2O/CO/NH3 ice matrices falls short in reproducing the highest observed interstellar abundances. In this case, at most 2.7% OCN- is formed with respect to H2O under conditions that no longer apply to a molecular cloud environment. On the other hand, photoprocessing and in particular thermal processing of solid HNCO in the presence of NH3 are very efficient OCN- formation mechanisms, converting 60%--85% and ~100%, respectively of the original HNCO. We propose that OCN- is most likely formed thermally from HNCO given the ease and efficiency of this mechanism. Upper limits on solid HNCO and the inferred interstellar ice temperatures are in agreement with this scenario.
We present Temperature Programmed Desorption (TPD) experiments of CO and N2 ices in pure, layered and mixed morphologies at various ice thicknesses and abundance ratios as well as simultaneously taken Reflection Absorption Infrared Spectra (RAIRS) of CO. A kinetic model has been developed to constrain the binding energies of CO and N2 in both pure and mixed environments and to derive the kinetics for desorption, mixing and segregation. For mixed ices N2 desorption occurs in a single step whereas for layered ices it proceeds in two steps, one corresponding to N2 desorption from a pure N2 ice environment and one corresponding to desorption from a mixed ice environment. The latter is dominant for astrophysically relevant ice thicknesses. The ratio of the binding energies, Rbe, for pure N2 and CO is found to be 0.936 +/- 0.03, and to be close to 1 for mixed ice fractions. The model is applied to astrophysically relevant conditions for cold pre-stellar cores and for protostars which start to heat their surroundings. The importance of treating CO desorption with zeroth rather than first order kinetics is shown. The experiments also provide lower limits of 0.87 +/- 0.05 for the sticking probabilities of CO-CO, N2-CO and N2-N2 ices at 14 K. The combined results from the desorption experiments, the kinetic model, and the sticking probability data lead to the conclusion that these solid-state processes of CO and N2 are very similar under astrophysically relevant conditions. This conclusion affects the explanations for the observed anti-correlations of gaseous CO and N2H+ in pre-stellar and protostellar cores.
The formation of double and triple C-C bonds from the processing of pure c-C6H12 (cyclohexane) and mixed H2O:NH3:c-C6H12 (1:0.3:0.7) ices by highly-charged, and energetic ions (219 MeV O^{7+} and 632 MeV Ni^{24+}) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ices analogs. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accelerateur National dIons Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared (FTIR) spectrometry at different ion fluences. Dissociation cross section of cyclohexane and its half-life in astrophysical environments were determined. A comparison between spectra of bombarded ices and young stellar sources indicates that the initial composition of grains in theses environments should contain a mixture of H2O, NH3, CO (or CO2), simple alkanes, and CH3OH. Several species containing double or triple bounds were identified in the radiochemical products, such as hexene, cyclohexene, benzene, OCN-, CO, CO2, as well as several aliphatic and aromatic alkenes and alkynes. The results suggest an alternative scenario for the production of unsaturated hydrocarbons and possibly aromatic rings (via dehydrogenation processes) in interstellar ices induced by cosmic ray bombardment.
CO$_2$ ice is an important reservoir of carbon and oxygen in star and planet forming regions. Together with water and CO, CO$_2$ sets the physical and chemical characteristics of interstellar icy grain mantles, including desorption and diffusion energies for other ice constituents. A detailed understanding of CO$_2$ ice spectroscopy is a prerequisite to characterize CO$_2$ interactions with other volatiles both in interstellar ices and in laboratory experiments of interstellar ice analogs. We report laboratory spectra of the CO$_2$ longitudinal optical (LO) phonon mode in pure CO$_2$ ice and in CO$_2$ ice mixtures with H$_2$O, CO, O$_2$ components. We show that the LO phonon mode position is sensitive to the mixing ratio of various ice components of astronomical interest. In the era of JWST, this characteristic could be used to constrain interstellar ice compositions and morphologies. More immediately, LO phonon mode spectroscopy provides a sensitive probe of ice mixing in the laboratory and should thus enable diffusion measurements with higher precision than has been previously possible.
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