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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 to an evolutionary track of the interstellar molecular clouds. H2O:CO (3:2) and (10:1) ices samples were irradiated by 0.79 MeV/u 58Ni13 + ions to simulate the effects produced by heavy ion cosmic rays in typical interstellar ices mixtures. The CO stretching vibration band is decomposed into six Gaussians functions (2150, 2144, 2141, 2138, 2136 and 2133 cm−1) and their integrated absorbances were measured as a function of fluence. The results have shown 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 ice in the ISM it is predicted that, after 1 Myrs, the main components of the CO stretching vibration band are the 2138 cm−1 and 2141 cm−1, due to the CO monomers and dimers, respectively.

International audience; N2O and CO2 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 (N2O) ice, and nitrous oxide and carbon dioxide (CO2) 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 N2O ice and the N2O:CO2 ice mixture are compared. The formation and dissociation cross sections scale with the electronic stopping power (Se) roughly as σ ∼ a Sen, where n ∼ 3/2. The n power law is helpful for predicting the N2O 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.

)3 Acetylene, C2H2, has been observed in the interstellar medium, mostly around young stellar objects, as well as in molecular clouds and cometary comae, representing an important species of astrophysical interest. In this work, we present a laboratory study of the C2H2 radiolysis at 45 K for three different beams and energies: 1.0 MeV H+ and He+, and 1.0 and 1.5 MeV N+ beams. Fourier transform infrared spectroscopy was used for monitoring the molecular changes induced by the ion processing. Two different sample thicknesses were irradiated; for the thicker one, implantation had occurred. Spectra and absorbance evolutions for the thin and thick films are qualitatively different. Four C2H2 bands are observed at 3225, 1954, 1392, and 763 cm−1. The C2H2 compaction and apparent destruction cross-sections are determined. For the case of the H+ beam, the compaction cross-section dominates. Concerning molecular synthesis by irradiation, New product bands were not observed in the thin ice irradiations; for the thicker film ice, the daughter species CH4, C2H4, C3H6, and C4H4 have been identified and their destruction and formation cross-sections determined. The apparent destruction cross-section was found to be a function of the electronic stopping power (Se) as σd ∝ S$_\mathrm{ e}^{3/2}$. The half-life of the C2H2 bombarded by galactic cosmic rays is estimated. The current findings are a contribution to the understanding of how the molecules synthesized upon irradiation of Interstellar and outer Solar system ices participate to the molecular enrichment and to the physicochemical evolution of the Universe.

International audience; Physico-chemical modifications induced by swift heavy ions on methane-water (CH 4 :H 2 O) ices at 15 K are analyzed. Ice films, at concentrations of (1:3) and (1:15), were irradiated by 40 MeV 58 Ni 11+ ions. Fourier transform transmission spectroscopy in the mid-range was used to monitor the evolution ices at 15 K as a function of projectile fluence. New IR bands appearing for the irradiated (CH 4 :H 2 O) (1:3) ice are attributed to the synthesized molecules: C 3 H 8 , HCO, H 2 CO, CO, CO 2 , H 2 O 2 , HCOOH, CH 3 OH, C 2 H 5 OH, and CH 3 CHO. For the irradiated (CH 4 :H 2 O) (1:15) ice, the abundances of the compounds containing two carbons atoms are lower than those for the (1:3) ice; in contrast, CH 3 OH and H 2 O 2 abundances increase when compared to the values obtained with the (1:3) ice. After irradiation, the ices were warmed up until 110 K, when the IR spectra reveal features of complex organic molecules. The destruction and formation cross sections and the sputtering yields of the ice mixtures are estimated. These findings provide possible pathways for the occurrence of compounds rich in C, O, and H, which are indeed observed in the cold regions of the universe such as ices in grain mantles of the interstellar medium and circumstellar envelopes.

Astronomical observations towards star-forming regions have revealed the presence of molecules with the N-O bond such as NO, N2O, and HNO. These species are considered potential precursors of prebiotic molecules. Thus, understanding nitrogen and oxygen chemistry may help us to better understand the origin and evolution of prebiotic molecules in space. However, species with the N-O bond are poorly studied and laboratory works on the effects induced on them by solar wind and galactic cosmic rays are still scarce. For this, we wanted to study the effects of ion bombardment on molecules with the N-O bond. We focus here on N2O ices and NO2:N2O4 = 1:1 ice mixtures (at 16 and 50/60 K) irradiated with 200 keV protons. Infrared transmission spectroscopy (8000-500 cm-1; 1.25-20 μm) was used to analyse the samples. Irradiation of N2O ices and NO2:N2O4 ice mixtures produces comparable effects independent of the irradiation temperature, NO being the main product. Moreover, we show that the maximum amount of N2O and N2O4 destroyed by irradiation, at the highest dose reached in our experiments, is equal to about 98 and 70 {{ per cent}}, respectively. The dose range covered in the experiments has been compared with the astrophysical time-scale of surface processing in space, showing that irradiation of N2O and NO2:N2O4 mixtures can produce, within 105-108 yr, amounts of solid NO ice detectable towards star-forming regions by the James Webb Space Telescope.

The matrix-isolated mid-IR (MIR) spectrum of neutral and ionized anthracoronene (C(36)H(18), AnthCor) in argon has been measured experimentally, compared to the spectrum of its parent molecules, coronene and anthracene, and analyzed by comparison to a theoretical spectrum computed using density functional theory (DFT). The experimental and theoretical band positions generally agree within 0–10 cm(−1). Anthracoronene exhibits extremely intense cation and anion bands around 1330 and 1318 cm(−1). The intensity of these two bands approaches what is traditionally observed in the entire 1000–1600 cm(−1) range for a typical PAH cation or anion. The matrix-isolated Near-IR (NIR) through Overlap Region (OVR) spectrum of ionized AnthCor in argon has been reported for the first time and compared to the spectrum of its parent molecules, coronene and anthracene. AnthCor cation contains a very strong electronic transition around 6175 cm(−1), placing it outside the range of the electronic transitions typically observed for PAHs. Anthracoronene is one of the few PAHs studied to-date which has exhibited the formation of anions upon UV photolysis.

A connection between the compaction of amorphous solid water (ASW) during energetic ion irradiation and the disappearing of water dangling bonds (OH-db) has been analyzed particularly by the Palumbo et al. and by Baragiola et al. In this work, a further discussion of the process for inducing the compaction is presented. Simple models for OH-db evolution for irradiated water ice are discussed. Literature results on the OH-db disappearance in ices bombarded by 100–200 keV H+ ions and on the comparison of porosity and OH-db results for 200 keV Ar+ ions are revisited. It is observed that for both, porosity decrease (compaction) and OH-db absorption signal decrease, experimental data can be well fitted by the sum of two decreasing exponentials with similar sets of parameters. Although a clear explanation for this correlation cannot be extracted, it suggests strongly that compaction and OH-db destruction are both triggered by two different processes.

Electronic sputtering of organic species being mixed to water ice by residual-gas condensation is analyzed by secondary ion time-of-flight mass spectrometry. The ice samples were prepared at 15 K by deposition from a H2O gas-flow and irradiated by 1.5 MeV N2+ ions while the temperature was raised up to 216 K. Desorption ion yields of positive H2O specific ions as of some organic ion species are measured as a function of temperature. Remarkably high desorption yield variations, mainly of the CnHm ions, were observed during the enrichment of organics hiding the emission of (H2O)nH3O+ cluster ions.

Methane (CH4) ice is found in the interstellar medium and in several bodies of the Solar system, where it is commonly exposed to cosmic rays and stellar winds. The chemical, physical and structural effects induced by fast heavy ions in thin layers of pure CH4 ices at 15 K are analysed by mid-infrared spectroscopy (Fourier transform infrared). Different pure CH4 ice samples were irradiated with 6 MeV 16 O 2 + , 220 MeV 16 O 7 + , 267 MeV 56 Fe 22 + and 606 MeV 70 Zn 26 + ions at Grand Acc´´ National d’Ions Lourds/France. Results show that CnHm molecules, where n = 2–4 and m = 2(n − 1) to 2(n + 1) and radical species CH3 ,C 2H3 and C2H5 are formed. The destruction cross-sections of CH4 ice and the formation cross-sections of new molecules CnHm are reported. The extrapolation of current results allow us to estimate the half lives of CH4 ices in the interstellar medium and the Solar system (Earth orbit) as about 600 × 10 6 and 600 yr, respectively. This huge ratio strongly suggests that the vast majority of

The chemical and physical effects induced by fast heavy ion irradiation on frozen pure methanol (CH3OH) at 15 K were studied. These energetic ions can simulate the energy transfer processes that occur by cosmic ray irradiation of interstellar ices, comets and icy Solar system bodies. The analysis was made by infrared spectroscopy (Fourier transform infrared) before and after irradiation, with 16-MeV 16O5+, 220-MeV 16O7+, 606-MeV 65Zn20+ and 774-MeV 86Kr31+ ion beams. Integrated values of the absorbance of the main methanol bands were determined. The induced CH3OH dissociation gives rise to the formation of molecular species, particularly H2CO, CH2OH, CH4, CO, CO2, HCO and HCOOCH3. Their formation and dissociation cross-sections were determined. H2CO and CH4 molecules are in general the most abundant new products of the four beams analysed. Except for the HCO and CH2OH species, cross-sections increased with the electronic stopping power, roughly as σ∼S3/2e. The G values for CH3OH destruction by fast heavy ion irradiation with Zn and Kr beams were found to be considerably larger than those for oxygen, helium or hydrogen. As an astrophysical implication, the S3/2e power law should be very helpful for predicting the CH3OH formation and dissociation cross-sections for other ion beam projectiles and energies. As astrophysical point of view, the analysis of the predictions reveals the unexpected importance of iron and some other heavy ion constituents of cosmic rays in astrochemistry.

Secondary ion emission from vapor-deposited water ice has been investigated in exploring the influence of phase transitions on the desorption yield of H2O ions, particularly, the hydronium H3O+ and the cluster ions (H2O)nH3O+. For 1.5 MeV N2+ ion bombardment on water ice at a temperature of ∼80 K, the sum of the yields of H3O+ and of the cluster ions represents 80% of the positive ion yield (i.e., 0.23 ions/impact) and 0.33% of the total H2O molecular sputtering yield. When the beam energy of N2+ is varied between 0.5 and 1.7 MeV, the shape of the cluster mass distributions does not change and the total cluster ion yield scales with the third power of the electronic energy loss. Time-of-flight mass spectra were taken during the warming up of the ice from 10 to 216 K. Up to 30 K, the cluster ion yields are approximately constant, whereas between 30 and 75 K, they decrease gradually by a factor 6.5 and remain constant until 130 K. This is in analogy with modifications in the ice structure: in the 38–78 K re...

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 14 K and irradiated by 28 keV 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, Yd (the number of ice molecules destroyed or dissociated per projectile impact), and the formation yield, Yf (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).

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International audience; The radiolysis of a mixture of acetone and nitrogen condensed at 13 K by 40-MeV 58Ni11 + ions was studied. The bombardment with heavy ions is highly efficient for inducing chemical reactions in ices. The disso-ciation rate of acetone mixed with nitrogen as a function of the fluence is determined from a sequence of infrared spectra. The formation of new molecular species due to the irradiation is investigated and their cross-sections are calculated.

Porous water ice and water ice mixtures H 2 O:X (X = CO, CO 2 and CH 4 ) produced at 15 K, with film thicknesses in the 0.5–1 μm range, were irradiated by swift ions and monitored by mid-infrared spectroscopy (FTIR). The analysis of the evolution of the pure water ice infrared absorption on ion beam dose reveals a strong correlation among three quantities: (i) the absorbance of the most intense band (3250 cm −1 ), (ii) the wavelength of the maximum absorbance of this band and (iii) the absorbance of the OH-dangling bonds. This correlation is interpreted as indications of the water ice compaction by irradiation: as the beam fluence increases, the ice porosity decreases, the dangling bond peaks collapse and the area and position of the 3250 cm −1 band vary exponentially, all of them evolving with the same compaction cross section ( σ c ). The linear dependence σ c ∝ S e ( S e being the electronic stopping power) is observed for both pure and mixed water ices, confirming previous results. We suggests that the infrared absorption A -value varies with dose as ( 1 - ζ e - D / D 0 ) during the compaction process ( D 0 = 0.2 eV/molec being the effective energy density to eliminate the OH-db, and ζ is a parameter characterizing the porosity). These findings may be used as a diagnostic tool to probe the morphology of water ices occurring in the outer Solar System and in the ISM.

Negative-ion beams have recently been suggested as sources of high-energy heavy atoms to be used as drivers for inertial confinement fusion (ICF). Owing to their electron affinities limited to a few eV, anions can be efficiently photo-detached in the vicinity of the fusion chamber, with the resulting high-velocity neutral projectiles following ballistic trajectories towards the hydrogen pellet target. Electron-detachment cross sections are needed as parameters to estimate the beam attenuation in the path from the ion source to the hydrogen pellet. Halogen anions are possible projectile choices. In this paper we present experimental data for total electron-detachment cross sections for F-, Cl-, Br - and I- ions incident on N 2 , in the 0.94-74 ke V u -1 energy range. Our measurements can benchmark theory on anion electron detachment at intermediate to high velocities. Comparison between different projectiles shows very similar collision velocity dependencies. A simple geometrical scaling is presented, providing an estimate for electron-detachment cross sections at the Me V u -1 energy range. The presented scaling indicates that the vacuum requirements due to the use of halogen anions for ICF are less critical than previously suggested.

Negative ion beams have been proposed as drivers for inertial confinement fusion (ICF), as high-velocity neutral projectiles produced by photodetachment may efficiently impact and heat up a hydrogen pellet target. Charge-changing cross sections are henceforth needed to estimate the beam attenuation in the residual gases. In this work we analyse cross section measurements for the several electron-loss collision channels of fluorine anions impinging on argon (10-50 keV/u energy range) and producing charge states from Ar + to Ar 4+ . Cross sections for projectile destruction associated to target ionization rise steeply with velocity, displaying a clear energy threshold. This threshold is characteristic of a collision process involving direct interaction between a projectile electron and a target electron.

We studied the effects produced by the interaction of heavy ion cosmic rays with interstellar and cometary organic molecules in the solid phase. Formic acid (HCOOH) ice at 15 K was irradiated by 267-MeV 56Fe22+ ions and the chemical evolution was analysed using Fourier transform infrared spectroscopy. The destruction cross-section of HCOOH and the formation cross-sections of the produced molecular species have been determined; the sputtering yield values are also discussed. The most abundant chemical species formed by Fe ion irradiation are CO, CO2 and H2O. The half-life of frozen formic acid molecules in the interstellar medium, as a result of interaction with the different cosmic ray constituents, is evaluated to be 108 yr, considering that the destruction cross-section σ d of heavy ions is ruled by a power law as a function of the electronic stopping power Se (i.e. σd ∼ S3/2 e ). Moreover, a complementary study based on mass spectrometry data from the literature has been performed, in order to understand the HCOOH molecule radiolysis, the desorption of its product and the chemical reaction pathways in ice.

Context. Cosmic ray ion irradiation affects the chemical composition of and triggers physical changes in interstellar ice mantles in space. One of the primary structural changes induced is the loss of porosity, and the mantles evolve toward a more compact amorphous state. Previously, ice compaction was monitored at low to moderate ion energies. The existence of a compaction threshold in stopping power has been suggested.Aims. In this article we experimentally study the effect of heavy ion irradiation at energies closer to true cosmic rays. This minimises extrapolation and allows a regime where electronic interaction always dominates to be explored, providing the ice compaction cross section over a wide range of electronic stopping power.Methods. High-energy ion irradiations provided by the GANIL accelerator, from the MeV up to the GeV range, are combined with in-situ infrared spectroscopy monitoring of ice mantles. We follow the IR spectral evolution of the ice as a function of increasing fluence (induced compaction of the initial microporous amorphous ice into a more compact amorphous phase). We use the number of OH dangling bonds of the water molecule, i.e. pending OH bonds not engaged in a hydrogen bond in the initially porous ice structure as a probe of the phase transition. These high-energy experiments are combined with lower energy experiments using light ions (H, He) from other facilities in Catania, Italy, and Washington, USA.Results. We evaluated the cross section for the disappearance of OH dangling bonds as a function of electronic stopping power. A cross-section law in a large energy range that includes data from different ice deposition setups is established. The relevant phase structuring time scale for the ice network is compared to interstellar chemical time scales using an astrophysical model.Conclusions. The presence of a threshold in compaction at low stopping power suggested in some previous works seems not to be confirmed for the high-energy cosmic rays encountered in interstellar space. Ice mantle porosity or pending bonds monitored by the OH dangling bonds is removed efficiently by cosmic rays. As a consequence, this considerably reduces the specific surface area available for surface chemical reactions.

Context. Several objects in the Solar System like Europa, Ganymede and Callisto have frozen surface (main component: H2O). The associated thickness is bigger than the penetration depth of the relevant projectile ions. Additionally, other species such as H2O2, SO2 and CO2 have been detected on these surface. The formation mechanisms of these molecules are still under discussion.\ud \ud Aims. We present new experimental results on the implantation of 13Cq+ (q = 2, 3) ions at an energy of 30 keV in water ice at low temperatures (15 and 80 K). Experiments with multiply charged ions at energies of tens of keV are particularly relevant to simulating the complexity of the irradiation environment to which the surfaces of the icy moons in the outer solar system are exposed.\ud \ud Methods. The experiments were performed at the low energy ion beam facility ARIBE of GANIL in Caen (France). 30 keV 13Cq+ (q =\ud 2, 3) ions have been used to bombard solid H,2O surface which were frozen at 15K and 80K. Fourier Transform Infrared Spectrometer (FTIR) was used to analyze the sample in the 5000 - 600 cm-1 (2-16.7 μm) region with a spectral resolution of 1 cm-1.\ud \ud Results. The results of our experiments indicate that implantation produces 13CO2 with yields in the range of 0.32-0.57 molecules ion-1. This yield seems to be independent of the temperature of the ices in the range studied. We have estimated the time scale necessary to accumulate by implantation of magnetospheric carbon ions the observed quantity of carbon dioxide on the surface of Europa, a Jovian moon. This time scale is of the order of 1.0-1.3x104 yrs which is higher than that evaluated for carbon dioxide production by other relevant processes.\ud \ud Conclusions.We conclude that although a relevant quantity of CO2 can be formed by carbon ion implantation, this is not the dominant formation mechanism at Europa.

Laboratory data of CH4 ice radiolysis promoted by fast heavy ions are obtained by infrared spectroscopy (FTIR). CH4 molecules are condensed on a CsI substrate at 15 K, and the ice layer is bombarded by 220 MeV 16 O 7+ ion beam. The ice thickness is thin enough to be traversed by projectiles at constant velocity close to the equilibrium charge state. The induced CH4 dissociation gives rise to the formation of molecular species CH3 ,C 2H2 ,C 2H4 ,C 2H6 ,a nd C 3H8. Their formation and dissociation cross sections are determined. C2H6 represent the most abundant daughter molecules. The carbon budget analysis of CH4 and its radiolysis products shows that the column density of carbon atoms contained in the methane destroyed during ion irradiation is 30−50% greater than the sum for the column densities of the newly formed species. As an astrophysical implication, the current results allow estimation of chemical reaction rates in ices covering interstellar grains.

Experimental measurements of the kinetic energy distribution spectra of ${\text{H}}^{+}$ fragment ions released during radiolysis of water molecules in collision with 20, 50, and 100 keV proton projectiles and 35, 200, 400, and 1000 eV electron projectiles are reported using a pulsed beam and drift tube time-of-flight based velocity measuring technique. The spectra show that ${\text{H}}^{+}$ fragments carrying a substantial amount of energy are released, some having energies well in excess of 20 eV. The majority of the ions lie within the 0--5 eV energy range with the proton spectra showing an almost constant profile between 1.5 and 5 eV and, below this, increasing gradually with decreasing ejection energy up to the near zero energy value while the electron spectra, in contrast, show a broad maximum between 1 and 3 eV and a pronounced dip around 0.25 eV. Beyond 5 eV, both projectile spectra show a decreasing profile with the electron spectra decreasing far more rapidly than the proton spectra. Our measured spectra thus indicate that major differences are present in the collision dynamics between the proton and the electron projectiles interacting with gas phase water molecules.

Time-of-flight mass spectrometry was used to investigate fragmentation and energy transfer processes in water by C ions at the distal part of the Bragg peak. Measurements of the positive ion fragments from ionization, electron capture, electron loss, transfer-loss and loss-ionization channels have allowed us for the first time (a) to obtain a quantitative determination of the energy lost by C ions in water and (b) to show that total water fragment ion production has a much flatter profile with projectile energy than would be expected if the water radical formation was assumed to follow the energy-loss profile obtained from available stopping power models.

Time-of-flight-based mass analysis of charged water fragments have been used to measure the dissociative and the nondissociative reaction pathways of water formed during collisions with 15 to 100 keV and 500 to 3500 keV H+ projectiles and with 8 to 100 keV H-0 projectiles. The fragmentation pathways resulting from the ionization and the electron capture collisions with the incident H+ and H-0 projectiles, as well as collisions involving projectile electron loss by the incident H-0 projectiles, were separately recorded by detecting the target product ions in coincidence with either the ejected target electrons or the charge-analyzed projectiles. The fragmentation profile shows that at high collision energies the ionization of water arises mainly through outer shell processes. At lower energies valence electron capture and ionization dominate and transfer ionization leads to substantially different fragmentation patterns. H-0 and H+ projectiles are found to be equally efficient at ionizing the water molecule. These results are of particular interest to workers in astrophysics and those involved in cancer therapy with heavy particle ion beams.

Single and double ionization processes for helium under the impact of B, O, and F anions were studied in the 1.1-1.9 a.u. velocity range. Coincidence cross sections were measured for direct ionization (DI), i.e., no projectile electron loss, and single (SL) and double projectile electron loss. The results show that DI is dominated by large impact parameters and SL is essentially the elastic scattering of the extra electron by the target. The cross section ratios taken between double and single helium ionization for single and double loss are projectile independent and grow almost linearly with the velocity.