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Context. In the cold and dense regions of the interstellar medium (ISM), for example in prestellar cores, gas-phase chemical abundances undergo a steep decrease due to the freeze-out of molecules onto the dust grain surfaces. While the depletion of many species would bring molecular abundances to undetected levels within short timescales, non-thermal desorption mechanisms such as UV photodesorption or cosmic-ray sputtering allows the return of a fraction of the ice mantle species back to the gas phase and prevents a complete freeze-out in the densest regions. In the last decade much effort has been devoted to understanding the microphysics of desorption and quantifying molecular desorption yields. Aims. H2CO is a ubiquitous molecule in the ISM and in the gas phase of prestellar cores, and is likely present in ice mantles, but its main desorption mechanism is unknown. In this paper our aim is to quantify the desorption efficiency of H2CO upon cosmic-ray impact in order to determine whether cosmic-ray induced sputtering could account for the H2CO abundance observed in prestellar cores. Methods. Using a heavy-ion beam as a cosmic-ray analogue at the Grand Accélérateur National d'Ions Lourds (GANIL) accelerator, we irradiated pure H2CO ice films at 10 K under high vacuum conditions and monitored the ice film evolution with infrared spectroscopy and the composition of the sputtered species in the gas phase using mass spectrometry. We derived both the effective and intact sputtering yield of pure H2CO ices. In addition, using IRAM millimetre observations, we also determined the H2CO gas-phase abundance in the prestellar core L1689B. Results. We find that H2CO easily polymerises under heavy-ion irradiation in the ice, and is also radiolysed into CO and CO2. In the gas phase, the dominant sputtered species is CO and intact H2CO is only a minor species. We determine an intact sputtering yield for pure H2CO ices of 2.5 × 103 molecules ion−1 for an electronic stopping power of Se ∼ 2830 eV (1015 molecules cm−2)−1. The corresponding cosmic-ray sputtering rate is ΓCRD = 1.5 × 1018ζ molecules cm−2 s−1, where ζ is the rate of cosmic-ray ionisation of molecular hydrogen in the ISM. In the frame of a simple steady-state chemical model of freeze-out and non-thermal desorption, we find that this experimental cosmic-ray sputtering rate is too low (by an order of magnitude) to account for the observed H2CO gas-phase abundance we derived in the prestellar core L1689B. We find however that this abundance can be reproduced if we assume that H2CO diluted in CO or CO2 ices co-desorbs at the same sputtering rate as pure CO or pure CO2 ices. [ABSTRACT FROM AUTHOR]

Aims. Astrophysical ices on dust grain mantles in the interstellar medium (ISM) and dense circumstellar envelopes (CSEs) are continuously exposed to galactic cosmic rays (GCRs). In a laboratory setting, we studied the physical and chemical modifications of ice layers induced by energetic heavy ions as GCR analogues. The ice layers used have a molecular composition similar to that of icy grain mantles. Methods. Mixtures of H2O:CO:CH3OH molecules (percentages 73:24:3, 68:30:3, and 58:38:3) were condensed on a substrate at 15 K and irradiated with 40 MeV 58Ni11+ ion beams. Irradiation-induced modifications were followed using the mid-infrared absorption spectroscopy technique. Results. We observed the evolution of infrared bands of CO2, HCO, HCOOH, CH4, H2CO,H2O2, and more complex synthesised molecules. From the molecular column densities, cross-sections and sputtering yields were determined and compared to published results of water and carbon monoxide. Analysis of the chemical modifications reveals that the precursors are easily destroyed when they are in a molecular mixture, while others are desorbed. Conclusions. The main radiolitic modifications induced by GCR irradiations are molecular decomposition and sputtering. Extrapolation to astrophysical radiation conditions shows a strong dependence on the intensity of the GCR distributions at low energies, which allows the analysis of the ice evolution at timescales comparable to those of the ISM and CSE. [ABSTRACT FROM AUTHOR]

Radiolysis of α-pinene by 61.3 MeV 84Kr15 + ions was analysed with the scope to simulate the effects of heavy ion cosmic ray bombardment on chiral molecules in the interstellar medium. The α-pinene ice samples were irradiated at 10 K and their chemical evolution was monitored by mid-infrared Fourier transform (FTIR) spectroscopy to characterize the reaction products and to determine the extent of racemization. The integrated band strengths have been obtained for all the neutral α-pinene vibrational bands using the experimental band integrated absorbances and the theoretical absolute intensities calculated along the column densities. In the current heavy ion bombardment experiments, small molecules were formed and the precursor, α-pinene, was destroyed instead of being racemized. Twelve hydrocarbons were produced (final fluence of 2.0 × 1012 ions cm−2): methane (CH4), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), propane (C3H8), n-butane (C4H10), butene (C4H8), propyne (C3H4), benzene (C6H6), ethane (C2H6), vinylacetylene (C4H4), and 2-methyl-1,3-butadiene or isoprene (C5H8). The highest formation cross-section (∼ 40 × 10−15 cm2) was observed for the C3H4 and the lowest was for C3H8 (∼ 3 × 10−15 cm2). The radiochemical yields for these molecules follow the same trends as those of their cross-sections. The atom budget calculation confirms that all the expected products have been generated during the radiolysis and supports the conclusion that the proposed A values are accurate. The α-pinene sputtering yield for this ion beam was found to be Y0  = 1.84 × 106 molecules per impact. [ABSTRACT FROM AUTHOR]

Carbon monoxide (CO) plays a vital role in interstellar chemistry, existing abundantly in both gaseous and frozen environments. Understanding the radiation-driven chemistry of CO-rich ices is crucial for comprehending the formation and desorption of C-bearing molecules in the interstellar medium (ISM), particularly considering the potential impact of temperature on these processes. We report experimental data on irradiation processing of pure CO ice by cosmic ray analogues (95.2 MeV 136Xe23+ ions) at temperatures of 10, 15, and 20 K, in the IGLIAS set-up coupled to the IRRSUD beamline at GANIL (Caen, France). The evolution of the irradiated frozen samples was monitored by infrared spectroscopy. The computational PROCODA code allows us to quantify the chemical evolution of the samples, determining effective reaction rates coefficients (ERCs), molecular abundances at the chemical equilibrium (CE) phase, and desorption processes. The model integrated 18 chemical species – 8 observed (CO, CO2, C3, O3, C2O, C3O, C3O2, and C5O3) and 10 non-observed but predicted (C, O, C2, O2, CO3, C4O, C5O, C2O2, C2O3, C4O2) – linked via 156 reactions. Our findings reveal temperature-driven influences on molecular abundances at chemical equilibrium, desorption yields and rates, and ERC values. Certain reaction routes exhibit distinct thermochemical behaviours of gas- and ice-phase reactions which may be attributed to the presence of neighbouring molecules within the ice matrix. This study provides pivotal insights into the chemical evolution of CO-enriched ice under irradiation, impacting solid-state astrochemistry, clarifying molecular abundances, and advancing our understanding of ISM chemistry and temperature effects on ionized radiation-processed frozen ices. [ABSTRACT FROM AUTHOR]

Aims. With this article, we aim to provide the sputtering yields for molecular species of potential astrophysical interest and in the electronic regime of interaction characteristic of cosmic rays. We specifically target molecules that are constitutive of interstellar ice mantles. Methods. We used a compendium of existing data on electronic sputtering to calculate the prefactors leading to the generalisation of the stopping-power-dependent sputtering yield for many species condensing at low temperature. In addition, we present new experimental results to constrain the yield for solid CH4, C6, and CH3CN. Results. Electronic sputtering is constrained using literature data for H2, HD, D2, Ne, N2, CO, Ar, O2, Kr, Xe, CO2, SO2, NH3, S, H2O, D2O, CH3OH, Leucine, C20H12, C24H12, and C60. A first-order relation with the sublimation enthalpy is derived, which allows us to predict the sputtering yield within an order of magnitude for most species. The fluctuations around the mean are partly assignable to the differences in resilience towards radiolysis for individual species, and partly to the micro-physics details of the energy transfer to the lattice. [ABSTRACT FROM AUTHOR]

H2O:CO, at concentrations of (3:2) and (10:1), was condensed on CsI substrate at 15 K and irradiated with 46-MeV 58Ni11 + ion beam. Radiolysis induced by fast heavy ions was analyzed by infrared spectroscopy (FTIR). The formation of nine molecular species: CO2, H2O2, HCOOH, HCO, H2CO, 13CO2, CH3OH, O3, and C3O2 was observed. For both concentrations, carbon dioxide (CO2), formaldehyde (H2CO), formic acid (HCOOH), and hydrogen peroxide (H2O2) are the most abundant products species, and tricarbon dioxide (C3O2) is much less abundant. Precursor destruction cross-sections and formation cross-sections of products are determined. The CO destruction cross-section for the (3:2) concentration is almost five times higher than that of water, while those for the (10:1) concentration are practically the same. Atomic sputtering yields are estimated for the two ice films, the total mass sputtered is approximately 2.5 × 106 u per impact. These results contribute to figure out the chemical pathways of compounds synthesized from the two most abundant organic species (H2O and CO) observed in the ices of grain mantles of the circumstellar envelopes and interstellar medium. In additional, the finding results reveal that molecular astronomical percentages are comparable to those obtained after 15 eV molec−1 of deposited dose in current experiments compared with the relative concentration of molecules in solid phase observed in MYSO, LYSO, BG Stars, and Comets. [ABSTRACT FROM AUTHOR]

The interstellar chemistry of nitrogen is considerably less understood than the chemistry of other common elements, such as carbon and oxygen. Even though a relatively large number of species containing nitrogen atoms have already been detected in the interstellar medium, only six of them bear a nitrogen–oxygen (N–O) bond. Some astrophysical and primeval Earth models suggest that N–O species, such as hydroxylamine (NH2OH), are potential precursors of prebiotic amino acids, and even peptides. In this work, we have analyzed an apolar ice mixture of N2:CO of astrophysical interest to investigate possible formation mechanisms of N–O bearing molecules due to processing of the sample by 64Ni24+ 538 MeV ions (8.4 MeV/u) at 14 K. The results show the formation of simple nitrogen oxides (⁠|$\rm {N_{1 - 2}}{O_y})$|⁠ , but no CN–O species of any kind. We have also determined the formation cross-sections of some of the products, as well as the destruction cross-sections of precursors and products. The results presented here are discussed in light of our previous work on the processing of a NH3:CO ice mixture, which have found no N–O bearing molecules at all. [ABSTRACT FROM AUTHOR]

H2O and CO molecules are the main constituents of the interstellar dust grain ice mantles. Infrared spectra of the ices in line of sights of young stellar objects and background stars have shown that the CO stretching vibration band can be decomposed into three main components: 2143, 2139, and 2136 cm−1, assigned to CO in different environment sites. The relative strengths between the components have been associated with an evolutionary track of the interstellar molecular clouds. H2O:CO (3:2) and (10:1) ice samples were irradiated by 0.79 MeV/u 58Ni13+ ions to simulate the effects produced by heavy ion cosmic rays in typical interstellar ice mixtures. The CO stretching vibration band is decomposed into six Gaussian functions (2150, 2144, 2141, 2138, 2136, and 2133 cm−1) and their integrated absorbances were measured as a function of fluence. The results show that, at the final fluence, the component 2138 cm−1 is the main component of the CO stretching vibration band. The component 2150 cm−1 disappears at the beginning of irradiation. Based on the present and previous results, a time-scale for the components in the interstellar ices is proposed. For H2O:CO ices in the interstellar medium, it is predicted that, after 1 Ma, the main components of the CO stretching vibration band are the 2138 and 2141 cm−1, due to the CO monomers and dimers, respectively. [ABSTRACT FROM AUTHOR]

Experimental results on the processing of NH3:CO ice mixtures of astrophysical relevance by energetic (538 MeV 64Ni24+) projectiles are presented. NH3 and CO are two molecules relatively common in interstellar medium and Solar system; they may be precursors of amino acids. 64Ni ions may be considered as representative of heavy cosmic ray analogues. Laboratory data were collected using mid-infrared Fourier transform spectroscopy and revealed the formation of ammonium cation (NH |$_4^+$|⁠), cyanate (OCN−), molecular nitrogen (N2), and CO2. Tentative assignments of carbamic acid (NH2COOH), formate ion (HCOO−), zwitterionic glycine (NH |$_3^+$| CH2COO−), and ammonium carbamate (NH |$_4^+$| NH2COO−) are proposed. Despite the confirmation on the synthesis of several complex species bearing C, H, O, and N atoms, no N–O-bearing species was detected. Moreover, parameters relevant for computational astrophysics, such as destruction and formation cross-sections, are determined for the precursor and the main detected species. Those values scale with the electronic stopping power (S e) roughly as σ ∼ a S |$_\mathrm{ e}^n$|⁠ , where n ∼ 3/2. The power law is helpful for predicting the CO and NH3 dissociation and CO2 formation cross-sections for other ions and energies; these predictions allow estimating the effects of the entire cosmic ray radiation field. [ABSTRACT FROM AUTHOR]

The processing of H2O:CO2:CH4 (10:1:1) and H2O:CO2:CH4:NH3 (10:1:1:1) ices at 72 K by oxygen ions was studied in an attempt to simulate the physicochemical effects induced by energetic ions on the surface of Enceladus (or similar cold surfaces in the outer Solar System). The experiments were carried out at the Grand Accélérateur National d'Ions Lourds (GANIL) in Caen/France. The samples were irradiated with 15.7-MeV O5+ at the IRRadiation SUD (IRRSUD) beamline and with 108-keV O6+ at the Accélérateurs pour les Recherches avec les Ions de Basses Energies (ARIBE) beamline. The frozen samples were monitored by Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy (4000–650 cm−1, 2.5–15.4 μm, at 1 cm−1 resolution). The identified molecular species formed during irradiation were CO, OCN−, CH3OH, HCN, CN−, H2CO3, HNCO, HCO and CO3. The effective formation cross-sections for the synthesis of new species and the effective molecular destruction cross-sections of the parent species in the experiments with MeV ions were found to be of the order of 10−14–10−13 cm2. For the keV ion experiments, these values were of the order of 10−16–10−15 cm2. The fluence at which the sample reaches chemical equilibrium and the molecular abundances in this region (equilibrium branching ratios) were estimated. These experiments suggest that the chemical inventory on the surface of Enceladus can be influenced by the incidence of charged particles on to the moon's surface. [ABSTRACT FROM AUTHOR]

Context. Micrometeorites represent, at timescales shorter than a few million years, the dominant source of extraterrestrial matter at the surface of the Earth. Analyses of ultracarbonaceous micrometeorites recovered from Antarctica, known as UCAMMs reveal an exceptionally N-rich organic matter associated with spatially extended high D enrichments. Experiments show that this specific organic matter might have been formed in the outer solar system by energetic irradiation of N-rich icy surfaces. Aims. We experimentally investigate the hydrogen isotopic fractionation resulting from irradiation of normal and D-rich N2-CH4 ices by high energy ions, simulating the exposition to Galactic cosmic rays of icy bodies surfaces orbiting at large heliocentric distances. Methods. Films of N2-CH4 ices and a N2-CH4/CD4/N2-CH4 "sandwich" ice were exposed to 129Xe13+ ion beams at 92 and 88 MeV. The chemical evolution of the samples was monitored using in situ Fourier transform infrared spectroscopy. After irradiation, targets were annealed to room temperature. The solid residues of the whole process left after ice sublimation were characterized in situ by infrared spectroscopy, and the hydrogen isotopic composition measured ex situ by imaging secondary ion mass spectrometry at the sub-micron scale (NanoSIMS). Results. Irradiation leads to the formation of new molecules and radicals. After annealing, the resulting poly-HCN-like macro-molecular residue exhibits an infrared spectrum close to that of UCAMMs. The residue resulting from irradiation of N2-CH4 ices does not exhibit a significant deuterium enrichment comparable to that found in extraterrestrial organic matter. The residue formed by irradiation of D-rich ices shows the formation of isotopic heterogeneities with localised hotspots and an extended contribution likely due to the diffusion of the radiolytic products from the D-rich layer. Conclusions. These results show that high-energy cosmic ray irradiation does not induce the large hydrogen isotopic fractionation observed at small spatial scale in interplanetary organics. By contrast, large D/H ratio heterogeneities at the sub-micron spatial scale in extraterrestrial organic matter can result from isotopically heterogeneous ices mixtures (i.e. condensed with different D/H ratios), which were transformed into refractory organic matter upon irradiation. [ABSTRACT FROM AUTHOR]

Context. The occurrence of complex organic molecules (COMs) in the gas phase at low temperature in the dense phases of the interstellar medium suggests that a non-thermal desorption mechanism is at work because otherwise, COMs should condense within a short timescale onto dust grains. Vacuum ultraviolet (VUV) photodesorption has been shown to be much less efficient for complex organic molecules, such as methanol, because mostly photoproducts are ejected. The induced photolysis competes with photodesorption for large COMs, which considerably lowers the efficiency to desorb intact molecules. Aims. We pursue an experimental work that has already shown that water molecules, the dominant ice mantle species, can be efficiently sputtered by cosmic rays. We investigate the sputtering efficiency of complex organic molecules that are observed either in the ice mantles of interstellar dense clouds directly by infrared spectroscopy (CH3OH), or that are observed in the gas phase by millimeter telescopes (CH3COOCH3) and that could be released from interstellar grain surfaces. Methods. We irradiated ice films containing complex organic molecules (methanol and methyl acetate) and water with swift heavy ions in the electronic sputtering regime. We monitored the infrared spectra of the film as well as the species released to the gas phase with a mass spectrometer. Results. We demonstrate that when methanol or methyl acetate is embedded in a water-ice mantle exposed to cosmic rays, a large portion is sputtered as an intact molecule, with a sputtering yield close to that of the main water-ice matrix. This must be even more true for the case of more volatile ice matrices, such as those that are embedded in carbon monoxide. Conclusions. Cosmic rays penetrating deep into dense clouds provide an efficient mechanism to desorb complex organic molecules. Compared to the VUV photons, which are induced by the interaction of cosmic rays, a large portion desorb as intact molecules with a proportion corresponding to the time-dependent bulk composition of the ice mantle, the latter evolving with time as a function of fluence due to the radiolysis of the bulk. [ABSTRACT FROM AUTHOR]

The radiolysis of 10:1 nitrogen:acetone mixture, condensed at 11 K, by 40 MeV 58Ni11+ ions is studied. These results are representative of studies concerning Solar system objects, such as transneptunian objects, exposed to cosmic rays. Bombardment by cosmic rays triggers chemical reactions leading to synthesis of larger molecules. In this work, destruction crosssections of acetone and nitrogen molecules in solid phase are determined and compared with those for pure acetone. The N2 column density decreases very fast indicating that, under irradiation, nitrogen leaves quickly a porous sample. The most abundant molecular species formed in the radiolysis are C3H6, C2H6, N3, CO, CH4 and CO2. Some N-bearing species are also formed, but with low production yield. Dissolving acetone in nitrogen decreases the formation cross-sections of CH4, CO2 and H2CO, while increases those for CO and C2H6 species. This fact may explain the presence of C2H6 in Pluto's surface where CH4 is not pure, but diluted in an N2 matrix. The formation of more complex molecules, such as HNCO and, possibly, glycine is observed, suggesting the formation of small prebiotic species in objects beyond Neptune from acetone diluted in a N2 matrix irradiated by cosmic rays. [ABSTRACT FROM AUTHOR]

Context. 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. Aims. 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. Methods. 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 Fourier transform infrared (FTIR) spectroscopy to investigate the induced effects. Results. The results indicate that ionic species such as HSO3−, HSO4−, and S2O52− are easily produced. Energetic processing also produces SO3 polymers and a sulfurous refractory residue. Conclusions. 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. In addition, we suggest that once expelled in the gas phase by sublimation, due to the temperature increase, and/or by non-thermal erosion those species would constitute a class of molecular ions not detected so far. We also suggest that molecular sulfur-bearing ions could be present on the surfaces and/or in the atmospheres of several objects in the solar system, for example icy satellites of the giant planets and comets. [ABSTRACT FROM AUTHOR]

The radiolysis of pure N2O ice at 11 and 75 K by 90 MeV 136Xe23+ ion irradiation has been studied by Fourier-transformed infrared spectroscopy (FTIR). Six daughter molecular species have been observed: NO2, (NO)2, N2O3, N2O4, N2O5, and O3. The chemical evolution of the new molecules formed in the sample was followed by the measurement of the column densities of the precursor and products as a function of the beam fluence. This procedure allows the determination of their formation and dissociation cross-sections. Other processes monitored by FTIR were sublimation (non-existent at 11 K, but present at 75 K) and ice compaction by the ion beam. Comparison between results obtained for the 11 and 75 K ices shows that formation and destruction cross-sections are higher (for light products) or much higher (for heavy products) at 75 K. This enhancement of chemical activity at higher temperature should not be attributed to higher projectile ionization rate but rather to a higher mobility of the radiolysis products in an ice undergoing slow sublimation. Although N2O ice has not yet been observed in space, it is reasonable to expect its occurrence since N and O are very abundant and reactive. Furthermore, if this ice is actually absent, the knowledge of the chemical-physical processes induced by ion irradiation on N2O ice at low temperature is necessary to explain its depletion. [ABSTRACT FROM AUTHOR]

In the dense and cold regions of the interstellar medium, molecules can be adsorbed on to dust grains to form ice mantles. Once formed, these can be processed by ionizing radiation coming from the stellar or interstellar medium, leading to the formation of several new molecules in the ice. Among the different types of ionizing radiation, cosmic rays play an important role in solid-phase chemistry because of the large amount of energy deposited in the ices. The physicochemical changes induced by the energetic processing of astrophysical ices are recorded in a intrinsic parameter of the matter called the complex refractive index. In this paper, for the first time, we present a catalogue containing 39 complex refractive indices (n, k) in the infrared from 5000 to 600 cm-1 (2.0-16.6 µm) for 13 different water-containing ices processed in the laboratory by cosmic ray analogues. The calculation was performed using the NKABS--an acronym of the determination of N and K from absorbance data--code, which employs the Lambert-Beer and Kramers-Kronig equations to calculate the values of n and k. The results are also available at the following web site: http://www1.univap.br/gaa/nkabs-database/data.htm. As a test case, H2O:NH3:CO2:CH4 ice was employed in a radiative transfer simulation of a protoplanetary disc to show that these data are indispensable to reproduce the spectrum of ices containing young stellar objects. [ABSTRACT FROM AUTHOR]

Context. Extraterrestrial materials, such as meteorites and interplanetary dust particles, provide constraints on the formation and evolution of organic matter in the young solar system. Micrometeorites represent the dominant source of extraterrestrial matter at the Earth’s surface, some of them originating from large heliocentric distances. Recent analyses of ultracarbonaceous micrometeorites recovered from Antarctica (UCAMMs) reveal an unusually nitrogen-rich organic matter. Such nitrogen-rich carbonaceous material could be formed in a N2-rich environment, at very low temperature, triggered by energetic processes. Aims. Several formation scenarios have been proposed for the formation of the N-rich organic matter observed in UCAMMs. We experimentally evaluate the scenario involving high energy irradiation of icy bodies subsurface orbiting at large heliocentric distances. Methods. The effect of Galactic cosmic ray (GCR) irradiation of ices containing N2 and CH4 was studied in the laboratory. The N2-CH4 (90:10 and 98:2) ice mixtures were irradiated at 14 K by 44 MeV Ni11+ and 160 MeV Ar15+ swift heavy ion beams. The evolution of the samples was monitored using in-situ Fourier transform infrared spectroscopy. The evolution of the initial ice molecules and new species formed were followed as a function of projectile fluence. After irradiation, the target was annealed to room temperature. The solid residue of the whole process left after ice sublimation was characterized in-situ by infrared spectroscopy, and the elemental composition was measured ex-situ. Results. The infrared bands that appear during irradiation allow us to identify molecules and radicals (HCN, CN− , NH3, ...). The infrared spectra of the solid residues measured at room temperature show similarities with that of UCAMMs. The results point towards the efficient production of a poly-HCN-like residue from the irradiation of N2-CH4 rich surfaces of icy bodies. The room temperature residue provides a viable precursor for the N-rich organic matter found in UCAMMs. [ABSTRACT FROM AUTHOR]

The chemical and physical effects induced by fast heavy-ion irradiation on a frozen mixture of methanol (CH3OH) and water (H2O) at 15 K are analysed. The laboratory experiment described here simulates the energy transfer processes that occur when cosmic rays bombard this particular ice mixture and helps to elucidate the understanding of the radiolysis of ices occurring in interstellar medium grains, at the surfaces of comets, and on icy Solar system bodies. Infrared spectroscopy (FTIR) was used before and during irradiation with a 40 MeV 58Ni11+ ion beam to determine the variation of the main absorption bands of methanol, water and products. In particular, the radiolysis of CH3OH:H2O (1:1) mixture leads to the formation of H2CO, CH4, CO, CO2, HCO and HCOOCH3. Their formation and dissociation cross-sections are determined. H2CO, CH4 and HCOOCH3 molecules have relatively high destruction cross-sections of around 9 × 10−13 cm2. Furthermore, atomic carbon, oxygen and hydrogen budgets are determined and used to verify the stoichiometry of the most abundant molecular species formed. Temperature effects are compared with irradiation effects, and the spectra of samples warmed-up to different temperatures are compared with those of the irradiated CH3OH:H2O mixtures. As an astrophysical application, the CH3OH:H2O dissociation cross-sections due to other ion beam projectiles and energies are predicted assuming validity of the Se3/2 power law; calculation of the integrated dissociation rates confirms the importance of nickel and some other heavy-ion constituents of cosmic rays in astrochemistry. [ABSTRACT FROM PUBLISHER]

Aims. The main goal of this work is to compare the effects induced in ices of astrophysical relevance by high-energy ions, simulating cosmic rays, and by vacuum ultraviolet (UV) photons. Methods. This comparison relies on in situ infrared spectroscopy of irradiated CH3OH:NH3 ice. Swift heavy ions were provided by the GANIL accelerator. The source of UV was a microwave-stimulated hydrogen flow discharge lamp. The deposited energy doses were similar for ion beams and UV photons to allow a direct comparison. Results. A variety of organic species was detected during irradiation and later during ice warm-up. These products are common to ion and UV irradiation for doses up to a few tens of eV per molecule. Only the relative abundance of the CO product, after ice irradiation, was clearly higher in the ion irradiation experiments. Conclusions. For some ice mixture compositions, the irradiation products formed depend only weakly on the type of irradiation, swift heavy ions, or UV photons. This simplifies the chemical modeling of energetic ice processing in space. [ABSTRACT FROM AUTHOR]

Cosmic rays are possibly the main agents to prevent the freeze-out of molecules onto grain surfaces in cold dense clouds. Ammonia (NH3) is one of the most abundant molecules present in dust ice mantles, with a concentration of up to 15% relative to water (H2O). FTIR spectroscopy is used to monitor pure NH3 and NH3-H2O ice samples as they are irradiated with Ni and Zn ion beams (500-600 MeV) at GANIL/France. New species, such as hydrazine (N2H4), diazene (N2H2 isomers), molecular hydrogen (H2), and nitrogen (N2) were identified after irradiation of pure NH3 ices. Nitrous oxide (N2O), nitrogen oxide (NO), nitrogen dioxide (NO2), and hydroxylamine (NH2OH) are some of the products of the NH3-H2O ice radiolysis. The spectral band at 6.85 μmwas observed after irradiation of both types of ice. Besides the likely contribution of ammonium (NH+4 ) and amino (NH2) radicals, data suggest a small contribution of NH2OH to this band profile after high fluences of irradiation of NH3-H2O ices. The spectral shift of the NH3 "umbrella" mode (9.3 μm) band is parameterized as a function of NH3/H2O ratio in amorphous ices. Ammonia and water destruction cross-sections are obtained, as well as the rate of NH3-H2O (1:10) ice compaction, measured by the OH dangling bond destruction cross-section. Ammonia destruction is enhanced in the presence of H2O in the ice and a power law relationship between stopping power and NH3 destruction cross-section is verified. Such results may provide relevant information for the evolution of molecular species in dense molecular clouds. [ABSTRACT FROM AUTHOR]

Context. Several molecular species have been observed as frozen gases in cold environments such as grains in the interstellar/circumstellar medium or icy objects in the outer solar system. Because N2 and O2 are homonuclear, symmetric molecules are not easily observed. It is therefore relevant to find indirect methods to prove their presence from astronomical observations. Aims. Here we investigate one of the possible indirect methods, namely the formation of specific molecules by cosmic ion bombardment of ices in astrophysical environments that contain O2 and N2. The observation of these molecules in astronomical environments could act as a trojan horse to detect the presence of frozen molecular oxygen and/or nitrogen. Methods. We have conducted ion bombardment experiments of frozen O2, H2O and their mixtures with N2 at the laboratories of CIMAP-GANIL at Caen (France) and LASp at Catania (Italy). Different ions (13C2+, Ar2+ and H+) and energies (30-200 keV) have been used. Results. We have found that 13CO2 is formed when carbon ions are implanted in ices containing H2O and/or O2. Ozone and nitrogen oxides (NO, N2O, NO2) are formed in the studied ices containing O2 and N2 with different relative abundances. Conclusions. We suggest that ozone and nitrogen oxides are present and have to be searched for in some specific environments such as dense clouds in the interstellar medium and the surfaces of Pluto, Charon and Triton. Their observation could demonstrate the presence of molecular oxygen and/or nitrogen. A possible interest for the observations of atmospheres in exo-planetary objects is also discussed. [ABSTRACT FROM AUTHOR]

ABSTRACT The formation of C=C and 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 16O7 + and 632-MeV 58Ni24 +) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ice analogues. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator Grand Accelératéur National d'Ions Lourds (GANIL) in Caen, France. The gas samples were deposited on to a polished CsI substrate previously cooled to 13 K. In situ analysis was performed by a Fourier transform infrared 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 these 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. [ABSTRACT FROM AUTHOR]

In order to simulate the effects of the heavy ion component of cosmic rays on ices in astrophysical environments, the CO and CO2 ices were irradiated with swift nickel ions in the electronic energy loss regime. The ices were prepared by condensing gas onto a CsI substrate at a temperature of 14 K and analyzed by means of infrared (FTIR) spectroscopy. The physical process of deposition by Ni ions is similar to more important and abundant heavy cosmic rays such as Fe ions. Dissociation of the ice molecules, and formation of new molecules were observed. Also, sputtering (leading to desorption of molecules from the solid surface to the gas phase) was observed. It was found that the sputtering yield due to heavy ions cannot be neglected with respect to desorption induced by weakly ionizing particles such as UV photons and protons. [ABSTRACT FROM PUBLISHER]

Thymine (C 5 H 6 N 2 O 2) is a basic N -heterocyclic nucleobase in all known organisms, and this molecule is also found in meteoritic materials. This study aims to investigate thymine's physical and chemical modifications under ion irradiation in cryogenic conditions. Space radiation was simulated by exposing thymine at 27 K to 230 MeV 48Ca10+ ions. Fourier transform infrared spectroscopy (FTIR) was employed to monitor the degradation of a 2.8 μm thick sample film under irradiation. From the intensity decrease of the infrared absorptions as a function of ion fluence, the destruction cross-section (σ), required to dissociate or eject a thymine molecule, is deduced by an exponential function. The physical and chemical modifications induced by energetic projectiles can be related to the electronic stopping power S e as σ = S e / D 0 , where D 0 = 9.6 ± 0.4 eV/molecule is the effective mean dose needed to destroy the thymine molecule at 27 K. Also, new molecular species formed under irradiation are observed and, based on infrared spectra, identified as CN−, OCN−, HCNO, and CO. [ABSTRACT FROM AUTHOR]

In the relatively shielded environments provided by interstellar dense clouds in our Galaxy, infrared astronomical observations have early revealed the presence of low temperature (10–100 K) ice mantles covering tiny grain “cores” composed of more refractory material. These ices are of specific interest because they constitute an interface between a solid phase under complex evolution triggered by energetic processes and surface reactions, with a rich chemistry taking place in the gas phase. The interstellar ice mantles present in these environments are immersed, in addition to other existing radiations fields, in a flux of cosmic ray particles that can produce new species via radiolysis processes, but first affects their structure, which may change and also induces desorption of molecules and radicals from these grains. Theses cosmic rays are simulated by swift ions in the laboratory for a better understanding of astrophysical processes. [ABSTRACT FROM AUTHOR]

N 2 O and CO 2 can be formed in the interstellar space and in ices on the surface of outer solar system bodies, such as Pluto and Triton. Energetic ions can simulate the energy transfer processes that occur by cosmic ray irradiation of interstellar ices, comets, and icy solar system bodies. Proceeding systematic research, pure nitrous oxide (N 2 O) ice, and nitrous oxide and carbon dioxide (CO 2) ice mixture were irradiated at 11 K with MeV-nitrogen (N+) and -xenon (Xe23+) ion beams. The chemical and physical effects induced by ion irradiation on the N 2 O ice and the N 2 O:CO 2 ice mixture are compared. The formation and dissociation cross sections scale with the electronic stopping power (S e) roughly as σ ∼ a S e n, where n ∼ 3/2. The n power law is helpful for predicting the N 2 O formation and dissociation cross-sections for other ion beam projectiles and energies; these predictions will allow estimating the effects of the entire cosmic ray radiation field. [ABSTRACT FROM AUTHOR]

Context. 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. Aims. 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. Methods. 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 Fourier transform infrared (FTIR) spectroscopy to investigate the induced effects. Results. The results indicate that ionic species such as HSO3−, HSO4−, and S2O52− are easily produced. Energetic processing also produces SO3 polymers and a sulfurous refractory residue. Conclusions. 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. In addition, we suggest that once expelled in the gas phase by sublimation, due to the temperature increase, and/or by non-thermal erosion those species would constitute a class of molecular ions not detected so far. We also suggest that molecular sulfur-bearing ions could be present on the surfaces and/or in the atmospheres of several objects in the solar system, for example icy satellites of the giant planets and comets. [ABSTRACT FROM AUTHOR]

Abstract: The effect of solar wind on cometary ice was studied by using oxygen ions with energy near to that corresponding to their maximum abundance in space for bombarding CO ice. This gas was condensed on a CsI substrate at 14K and irradiated by 28keV 18O6+ ions up to a final fluence of 1.3×1016 cm−2. We have used a methodology in which the sputtering yields, the destruction rate of CO, and the rate of formation of new molecular species are determined by Fourier transform infrared spectroscopy (FTIR). In the current experiment, the condensation of a thin water ice film has prevented the CO sputtering. Quantities such as the dissociation yield, Y d (the number of ice molecules destroyed or dissociated per projectile impact), and the formation yield, Y f (the number of daughter molecules of a given species formed per projectile) are found to be more appropriate and useful than using an integrated or average cross section, since the projectiles are slowing down in the ice from their initial energy until zero velocity (implantation). [Copyright &y& Elsevier]

The synthesis of methylenimine and cyanomethanimine from ion irradiation of N 2 -CH 4 ice was studied, in an attempt to simulate the role of medium mass cosmic rays and energetic solar particles in the processing of nitrogen-rich ices on cold astrophysical environments, such as those in the outer region of the solar system (e.g. Pluto, Charon, Triton, Makemake and Titan). The N 2 -CH 4 (90:10) ice mixture was irradiated at 9 K by 38.4 MeV 40Ca9+ (0.96 MeV/u) at the GANIL facility (Caen/Fance). The evolution of the samples was monitored using in-situ Fourier transform infrared spectroscopy (FTIR). The results indicate the formation of CH 2 NH and CH 2 NCN, which are considered species of interest in prebiotic chemistry. Other species produced by radiolysis were HCN, HNC, hydrocarbons and nitriles. Direct comparison of the laboratory spectrum from the mixture of reaction products provides an efficient way to focus on the identification of chemical synthesis routes for the production of molecules important in the development of life that are consistent with the chemical inventory and physical conditions on frozen moons and cold objects in the outer solar system. Unlabelled Image • We reported results of ion irradiation of N 2 -CH 4 ice mixture. • Several C-N compounds are identified, including methylenimine and cyanomethanimine. • Possible formation mechanisms of prebiotic species, such as adenine (C 5 H 5 N 5) • Implications for formation of prebiotic molecules in the outer solar system. [ABSTRACT FROM AUTHOR]