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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. Using a heavy-ion beam as a cosmic-ray analogue at the 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. 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 $2.5\times 10^3$ molecules ion$^{-1}$ for an electronic stopping power of $S_e\sim2830$ eV ($10^{15}$ molecules cm$^{-2}$)$^{-1}$. The corresponding cosmic-ray sputtering rate is $\Gamma_\mathrm{CRD}=1.5\times 10^{18}\zeta$ molecules cm$^{-2}$ s$^{-1}$, where $\zeta$ 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., Comment: accepted by Astronomy and Astrophysics. 17 pages, 17 figures. Abridged abstract

We have performed classical molecular dynamics simulations of 3 keV Ar + $(\mathrm{C}_{24}\mathrm{H}_{12})_n(\mathrm{C}_{60})_{m}$ collisions where $(n,m)=(3,2), (1,4), (9,4)$ and $(2,11)$. The simulated mass spectra of covalently bound reaction products reproduce the main features of the corresponding experimental results reported by Domaracka et al., PCCP, 2018, 20, 15052. The present results support their conclusion that molecular growth is mainly driven by knockout where individual atoms are promptly removed in Rutherford type scattering processes. The so formed highly reactive fragments may then bind with neighboring molecules in the clusters producing a rich variety of growth products extending up to sizes containing several hundreds of atoms, and here we show examples of such structures. In addition, knocked out atoms may be absorbed such that e.g. hydrogenated coronene and fullerene molecules are formed., Comment: 7 pages, 7 figures

Methanol ice is embedded in interstellar ice mantles present in dense molecular clouds. We aim to measure the sputtering efficiencies starting from different ice mantles of varying compositions experimentally, in order to evaluate their potential impact on astrochemical models. The sputtering yields of complex organic molecules is of particular interest, since few mechanisms are efficient enough to induce a significant feedback to the gas phase. We irradiated methanol and carbon dioxide ice mixtures of varying ratios with swift heavy ions in the electronic sputtering regime. We monitored the evolution of the infrared spectra and the species released to the gas phase with a mass spectrometer. Methanol and 13C-methanol isotopologue were used to remove any ambiguity on the measured irradiation products. The sputtering of methanol embedded in carbon dioxide ice is an efficient process leading to the ejection of intact methanol in the gas phase. We establish that when methanol is embedded in a carbon-dioxide-rich mantle exposed to cosmic rays, a significant fraction is sputtered as intact molecules. The sputtered fraction follows the time-dependent bulk composition of the ice mantle, the latter evolving with time due to the radiolysis-induced evolution of the bulk. If methanol is embedded in a carbon dioxide ice matrix, as the analyses of the spectral shape of the CO2 bending mode observations in some lines of sight suggest, the overall methanol sputtering yield is higher than if embedded in a water ice mantle. The sputtering is increased by a factor close to the dominant ice matrix sputtering yield, which is about six times higher for pure carbon dioxide ice when compared to water ice. These experiments are further constraining the cosmic-ray-induced ice mantle sputtering mechanisms important role in the gas-phase release of complex organic molecules from the interstellar solid phase., Comment: arXiv admin note: text overlap with arXiv:1906.03084

The occurrence of complex organic molecules (COMs) in the gas phase at low temperature in the dense phases of the ISM suggests that a non-thermal desorption mechanism is at work because otherwise, COMs should condense within a short timescale onto dust grains. Vacuum ultraviolet 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, considerably lowering the efficiency to desorb intact molecules. 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. 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. 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 more volatile ice matrices, such as those that are embedded in carbon monoxide. Cosmic rays penetrating deep into dense clouds provide an efficient mechanism to desorb complex organic molecules. Compared to VUV photons 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., Comment: Corrected a copy/paste typo in Table 2: The CO2 stretch A value is 7.6d-17 Gerakines et al. (1995), replacing 1.8d-17 D'Hendecourt & Allamandola (1986)

Interstellar grain mantles present in dense interstellar clouds are in constant exchange with the gas phase via accretion and desorption mechanisms such as UV, X-ray photodesorption, cosmic ray induced sputtering, grain thermal fluctuations, and chemical reaction energy release. The relative importance of the various desorption mechanisms is of uttermost importance for astrophysical models to constrain the chemical evolution in such high density dense cloud regions. In this experimental work we investigated the sputtering yield as a function of ice mantle thickness, exposed to Xe ions at 95MeV. The ion induced ice phase transformation and the sputtering yield were simultaneously monitored by IR spectroscopy and mass spec- trometry, respectively. The sputtering yield is constant above a characteristic ice layer thickness and starts to decrease below this thickness. An estimate of the sputtering depth corresponding to this length can be evaluated. In these experiments the measured desorption depth corresponds to 30 ice layers. Assuming an effective cylindrical shape for the volume of sputtered molecules, the aspect ratio is close to unity; in the semi-infinite ice film case this ratio is the diameter to height of the cylinder. This result shows that most ejected molecules arise from a rather compact volume. The measured infinite thickness sputtering yield for water ice mantles scales as the square of the ion electronic stopping power (Se). We expect that the desorption depth dependence varies with Se^a , where a=0.5. Astrophysical models should take into account the thickness dependence constraints of these ice mantles in the interface regions when ices are close to their extinction threshold. In the very dense cloud regions, most of the water ice mantles are above this limit for the bulk of the cosmic rays., Comment: 6 pages, 5 figures

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.

We report on studies of collisions between 3 keV Ar$^+$ projectile ions and neutral targets of isolated 1,3-butadiene (C$_4$H$_6$) molecules and cold, loosely bound clusters of these molecules. We identify molecular growth processes within the molecular clusters that appears to be driven by knockout processes and that could result in the formation of (aromatic) ring structures. These types of reactions are not unique to specific projectile ions and target molecules, but will occur whenever atoms or ions with suitable masses and kinetic energies collide with aggregates of matter, such as carbonaceous grains in the interstellar medium or aerosol nanoparticles in the atmosphere., Comment: 8 pages, 6 figures, Accepted for publication in Physical Chemistry Chemical Physics 2017

Under cosmic irradiation, the interstellar water ice mantles evolve towards a compact amorphous state. Crystalline ice amorphisation was previously monitored mainly in the keV to hundreds of keV ion energies. We experimentally investigate heavy ion irradiation amorphisation of crystalline ice, at high energies closer to true cosmic rays, and explore the water-ice sputtering yield. We irradiated thin crystalline ice films with MeV to GeV swift ion beams, produced at the GANIL accelerator. The ice infrared spectral evolution as a function of fluence is monitored with in-situ infrared spectroscopy (induced amorphisation of the initial crystalline state into a compact amorphous phase). The crystalline ice amorphisation cross-section is measured in the high electronic stopping-power range for different temperatures. At large fluence, the ice sputtering is measured on the infrared spectra, and the fitted sputtering-yield dependence, combined with previous measurements, is quadratic over three decades of electronic stopping power. The final state of cosmic ray irradiation for porous amorphous and crystalline ice, as monitored by infrared spectroscopy, is the same, but with a large difference in cross-section, hence in time scale in an astrophysical context. The cosmic ray water-ice sputtering rates compete with the UV photodesorption yields reported in the literature. The prevalence of direct cosmic ray sputtering over cosmic-ray induced photons photodesorption may be particularly true for ices strongly bonded to the ice mantles surfaces, such as hydrogen-bonded ice structures or more generally the so-called polar ices., Comment: 22pages, 11 figures, accepted in A&A

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. 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. 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. 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., Comment: 9 pages, 9 figures, 2 tables, accepted in A&A

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 Accel\'erat\'eur National d'Ions 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., Comment: 14 pages, 10 figures, 4 tables. Accepted to be published in MNRAS

An experimental study on the interaction of heavy, highly charged, and energetic ions (52 MeV Ni^13+) with pure H2O, pure CO2 and mixed H2O:CO2 astrophysical ice analogs is presented. This analysis aims to simulate the chemical and the physicochemical interactions induced by heavy cosmic rays inside dense and cold astrophysical environments such as molecular clouds or protostellar clouds. The measurements were performed at the heavy ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds in Caen, France). The gas samples were deposited onto a CsI substrate at 13 K. In-situ analysis was performed by a Fourier transform infrared (FTIR) spectrometer at different fluences. Radiolysis yields of the produced species were quantified. The dissociation cross sections of pure H2O and CO2 ices are 1.1 and 1.9E-13 cm^2, respectively. In the case of mixed H2O:CO2 (10:1) the dissociation cross sections of both species are about 1E-13 cm^2. The measured sputtering yield of pure CO2 ice is 2.2E4 molec/ion. After a fluence of 2-3E12 ions/cm^2 the CO2/CO ratio becomes roughly constant (~0.1), independent of the of initial CO2/H2O ratio. A similar behavior is observed for the H2O2/H2O ratio which stabilizes at 0.01, independent of the initial H2O column density or relative abundance., Comment: 13 pages, 9 figures, 4 tables. Accepted to be published in Astronomy and Astrophysics

Deeply inside dense molecular clouds and protostellar disks, the interstellar ices are protected from stellar energetic UV photons. However, X-rays and energetic cosmic rays can penetrate inside these regions triggering chemical reactions, molecular dissociation and evaporation processes. We present experimental studies on the interaction of heavy, highly charged and energetic ions (46 MeV Ni^13+) with ammonia-containing ices in an attempt to simulate the physical chemistry induced by heavy ion cosmic rays inside dense astrophysical environments. The measurements were performed inside a high vacuum chamber coupled to the heavy ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France.\textit{In-situ} analysis is performed by a Fourier transform infrared spectrometer (FTIR) at different fluences. The averaged values for the dissociation cross section of water, ammonia and carbon monoxide due to heavy cosmic ray ion analogs are ~2x10^{-13}, 1.4x10^{-13} and 1.9x10^{-13} cm$^2$, respectively. In the presence of a typical heavy cosmic ray field, the estimated half life for the studied species is 2-3x10^6 years. The ice compaction (micropore collapse) due to heavy cosmic rays seems to be at least 3 orders of magnitude higher than the one promoted by (0.8 MeV) protons . In the case of the irradiated H2O:NH3:CO ice, the infrared spectrum at room temperature reveals five bands that were tentatively assigned to vibration modes of the zwitterionic glycine (+NH3CH2COO-)., Comment: Accepted to be published in Astronomy and Astrophysics; Number of pages: 12; Number of Figures: 7; Number of Tables: 5