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Register a new userThe thermal reactivity of HCN and NH3 in interstellar ice analogues
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HCN is a molecule central to interstellar chemistry, since it is the simplest molecule containing a carbon-nitrogen bond and its solid state chemistry is rich. The aim of this work was to study the NH3 + HCN -> NH4+CN- thermal reaction in interstellar ice analogues. Laboratory experiments based on Fourier transform infrared spectroscopy and mass spectrometry were performed to characterise the NH4+CN- reaction product and its formation kinetics. This reaction is purely thermal and can occur at low temperatures in interstellar ices without requiring non-thermal processing by photons, electrons or cosmic rays. The reaction rate constant has a temperature dependence of k(T) = 0.016+0.010-0.006 s-1.exp((-2.7+-0.4 kJmol-1)/(RT)) when NH3 is much more abundant than HCN. When both reactants are diluted in water ice, the reaction is slowed down. We have estimated the CN- ion band strength to be A_CN- = 1.8+-1.5 x10-17 cm molec-1 at both 20 K and 140 K. NH4+CN- exhibits zeroth-order multilayer desorption kinetics with a rate of k_des(T) = 10^28 molecules cm-2 s-1.exp((-38.0+-1.4 kJmol-1)/(RT)). The NH3 + HCN -> NH4+CN- thermal reaction is of primary importance because (i) it decreases the amount of HCN available to be hydrogenated into CH2NH, (ii) the NH4+ and CN- ions react with species such as H2CO, or CH2NH to form complex molecules, and (iii) NH4+CN- is a reservoir of NH3 and HCN, which can be made available to a high temperature chemistry.
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Context. The molecular composition of interstellar ice mantles is defined by gas-grain processes in molecular clouds, with the main components being $H_2O$, $CO$, and $CO_2$. $CH_3OH$ ice is detected towards the denser regions, where large amounts of $CO$ freeze out and get hydrogenated. Heating from nearby protostars can further change the ice structure and composition. Despite the several observations of icy features towards molecular clouds and along the line of site of protostars, it is not yet clear if interstellar ices are mixed or if they have a layered structure. Aims. We aim to examine the effect of mixed and layered ice growth in ice mantle analogues, with focus on the position and shape of methanol infrared bands, so future observations could shed light on the structure of interstellar ices in different environments. Methods. Mixed and layered ice samples were deposited on a cold substrate kept at T = 10 K using a closed-cycle cryostat placed in a vacuum chamber. The spectroscopic features were analysed by FTIR spectroscopy. Different proportions of the most abundant four molecules in ice mantles, namely $H_2O$, $CO$, $CO_2$, and $CH_3OH$, were investigated, with special attention on the analysis of the $CH_3OH$ bands. Results. We measure changes in the position and shape of the CH and CO stretching bands of $CH_3OH$ depending on the mixed or layered nature of the ice sample. Spectroscopic features of methanol are also found to change due to heating. Conclusions. A layered ice structure best reproduces the $CH_3OH$ band position recently observed towards a pre-stellar core and in star-forming regions. Based on our experimental results, we conclude that observations of $CH_3OH$ ices can provide information about the structure of interstellar ices, and we expect JWST to put stringent constraints on the layered or mixed nature of ices in different interstellar environments.
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.
Formic acid (HCOOH) has been extensively detected in space environments, including interstellar medium (gas and grains), comets and meteorites. Such environments are often subjected to the action of ionizing agents, which may cause changes in the molecular structure, thus leading to formation of new species. Formic acid is a possible precursor of pre-biotic species, such as Glycine (NH2CH2COOH). This work investigates experimentally the physicochemical effects resulting from interaction of heavy and energetic cosmic ray analogues (46MeV 58Ni11+) in H2O:HCOOH (1:1) ice, at 15 K, in ultrahigh vacuum regime, using Fourier transform infrared spectrometry in the mid-infrared region (4000-600 cm-1 or 2.5-12.5 microns). After the bombardment, the sample was slowly heated to room temperature. The results show the dissociation cross-section for the formic acid of 2.4x10^-13 cm2, and half-life due to galactic cosmic rays of 8x10^7 yr. The IR spectra show intense formation of CO and CO2, and small production of more complex species at high fluences.
Escalating observations of exo-minor planets and their destroyed remnants both passing through the solar system and within white dwarf planetary systems motivate an understanding of the orbital history and fate of exo-Kuiper belts and planetesimal discs. Here we explore how the structure of a 40-1000 au annulus of planetesimals orbiting inside of a solar system analogue that is itself initially embedded within a stellar cluster environment varies as the star evolves through all of its stellar phases. We attempt this computationally challenging link in four parts: (1) by performing stellar cluster simulations lasting 100 Myr, (2) by making assumptions about the subsequent quiescent 11 Gyr main-sequence evolution, (3) by performing simulations throughout the giant branch phases of evolution, and (4) by making assumptions about the belts evolution during the white dwarf phase. Throughout these stages, we estimate the planetesimals gravitational responses to analogues of the four solar system giant planets, as well as to collisional grinding, Galactic tides, stellar flybys, and stellar radiation. We find that the imprint of stellar cluster dynamics on the architecture of $gtrsim 100$ km-sized exo-Kuiper belt planetesimals is retained throughout all phases of stellar evolution unless violent gravitational instabilities are triggered either (1) amongst the giant planets, or (2) due to a close ($ll 10^3$ au) stellar flyby. In the absence of these instabilities, these minor planets simply double their semimajor axis while retaining their primordial post-cluster eccentricity and inclination distributions, with implications for the free-floating planetesimal population and metal-polluted white dwarfs.
Interstellar Objects (ISO) passing through our Solar System offer a rare opportunity to probe the physical and chemical processes involved in solid body and planet formation in extrasolar systems. The main objective of our study is to search for diagnostic absorption features of water ice in the near infrared (NIR) spectrum of the second interstellar object 2I/2019 Q4 (Borisov) and compare its ice features to those of the Solar system icy objects. We observed 2I in the NIR on three separate occasions. The first observation was made on 2019 September 19 UT using the SpeX spectrograph at the 3-m IRTF and again on September 24 UT with the GNIRS spectrograph at the 8-m GEMINI telescope and the last observation was made on October 09 UT with IRTF. The spectra obtained from all three nights appear featureless. No absorption features associated with water ice are detected. Spectral modeling suggests that water grains, if present, comprise no more than 10% of the coma cross-section. The comet consistently exhibits a red D-type like spectrum with a spectral slope of about 6% per 100nm, which is similar to that of 1I/Oumuamua and is comparable to Solar system comets.
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