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This roadmap article highlights recent advances, challenges and future prospects in studies of the dynamics of molecules and clusters in the gas phase. It comprises nineteen contributions by scientists with leading expertise in complementary experimental and theoretical techniques to probe the dynamics on timescales spanning twenty order of magnitudes, from attoseconds to minutes and beyond, and for systems ranging in complexity from the smallest (diatomic) molecules to clusters and nanoparticles. Combining some of these techniques opens up new avenues to unravel hitherto unexplored reaction pathways and mechanisms, and to establish their significance in, e.g. radiotherapy and radiation damage on the nanoscale, astrophysics, astrochemistry and atmospheric science. [ABSTRACT FROM AUTHOR]

The article discusses the Multiple Beam Irradiation Platform (MIRRPLA), a new instrument being developed in France to study the origin and evolution of organic matter in the solar system. The platform will simulate a realistic space radiation field by irradiating ice layers with multiple types of radiation, including UV photons, electrons, and ions. The complex organic molecules formed during irradiation will be detected and analyzed using various techniques. MIRRPLA will be open to scientists from different fields and industries. The article also mentions the potential applications of MIRRPLA in cancer treatment, environmental science, and materials science. [Extracted from the article]

Electron-scattering cross sections have been determined for trimethylene oxide, cyclic (CH2)3O molecule, both experimentally and theoretically. The absolute total cross section (TCS) has been measured over energies from 1 to 400 eV using a linear electron-transmission method. The obtained TCS generally decreases with rising energy, except for the 3–10 eV range, where some resonantlike structures are discernible. Integral elastic cross section (ECS) and ionization cross section (ICS) have been also calculated up to 3 keV in the additivity rule approximation and the binary-encounter-Bethe approach, respectively. Their sum, ECS+ICS, is in a good agreement with the measured TCS. Comparison of the TCS energy dependence for trimethylene oxide with that for its isomeric open-chain counterpart—acetone, (CH3)2CO, has also been made. Moreover, examination of experimental TCSs for the cyclic (CH2)nO, n=2–4, ether series reveals that the intermediate-energy molecular TCSs for members of that family can be nicely represented as a sum of the effective TCSs for particular constituents of the molecule, i.e., methylene groups and oxygen atom. Finally, based on these partial TCSs, the TCS for the c-(CH2)5O—the next member of the series—has been determined and compared with the respective ECS+ICS values computed here for this compound. [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]

Abstract: The results of an experimental investigation of 1keV electron irradiation of ices (deposited at 30K) of (i) pure methanol and (ii) of a 1:1 mixture of NH3:CH3OH are reported. Molecular products formed within the ice were detected and monitored using FTIR spectroscopy. The products observed were methyl formate (H3COHCO), methane (CH4), hydroxymethyl (CH2OH), formamide (HCONH2), formic acid (HCOOH), formaldehyde (H2CO), formyl radical (HCO), cyanate ion (OCN−), isocyanic acid (HNCO), carbon monoxide (CO) and carbon dioxide (CO2). The consequences of these results for prebiotic chemistry in the interstellar medium and star forming regions are discussed. [Copyright &y& Elsevier]

ABSTRACT 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∼ S3/2 e. 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 S3/2 e 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. [ABSTRACT FROM AUTHOR]

Abstract: Water, carbon oxide, carbon dioxide, and ammonia ices are known to be pervasive constituents of the solar system and the interstellar medium. These ices and ice-covered surfaces are exposed to bombardment by energetic projectiles like photons, electrons, and ions. Laboratory experiments have been carried out to study the effects of such irradiation. However, there is a clear lack of information about the interaction of heavy ion components of solar/stellar wind and galactic cosmic rays (e.g. Fe) with ices in the keV to GeV energy range. The objective of this work is to study the effects produced in astrophysical ices by highly charged nickel ions at relatively high energy (∼50–500MeV) in the electronic energy loss regime, and to compare them with those produced by protons, photons, and electrons. Our results for and CO indicate that sputtering induced by heavy ions can be an important mechanism to desorb molecules in astrophysical environments. [ABSTRACT FROM AUTHOR]

Abstract: The absolute total cross-section (TCS) for electron scattering from α-tetrahydrofurfuryl alcohol (C5H10O2; THFA) has been measured using the linear transmission technique for energies ranging from 1 to 370eV. The obtained TCS function has the relatively high magnitude over the whole energy range studied. That is also characterized by the broad enhancement spanned between 3.5 and 15eV superimposed with two distinct resonant-like structures. Additional weak structures can be distinguished below 3eV while two other features are discernible above ionization threshold. The present TCS is compared with available experimental and theoretical cross section data. [Copyright &y& Elsevier]

Abstract: In this work, we study the modification of hydrogenated diamond films deposited on silicon resulting from its exposure to DBr followed by an annealing above 600K, using high resolution electron energy loss spectroscopy (HREELS). This procedure results in silicon carbide SiC formation within the diamond film, as evidenced by the observation of a loss peak at 117meV and its first harmonic at 233meV in HREEL spectra. This diamond surface modification is interpreted as resulting from the reaction of products of the silicon support thermally activated etching with hydrogenated diamond. [Copyright &y& Elsevier]

The valence ionization of uracil and mixed water–uracil clusters has been studied experimentally and by ab initio calculations. In both measurements, the spectrum onset shows a red shift with respect to the uracil molecule, with the mixed cluster characterized by peculiar features unexplained by the sum of independent contributions of the water or uracil aggregation. To interpret and assign all the contributions, we performed a series of multi-level calculations, starting from an exploration of several cluster structures using automated conformer-search algorithms based on a tight-binding approach. Ionization energies have been assessed on smaller clusters via a comparison between accurate wavefunction-based approaches and cost-effective DFT-based simulations, the latter of which were applied to clusters up to 12 uracil and 36 water molecules. The results confirm that (i) the bottom-up approach based on a multilevel method [Mattioli et al. Phys. Chem. Chem. Phys. 23, 1859 (2021)] to the structure of neutral clusters of unknown experimental composition converges to precise structure–property relationships and (ii) the coexistence of pure and mixed clusters in the water–uracil samples. A natural bond orbital (NBO) analysis performed on a subset of clusters highlighted the special role of H-bonds in the formation of the aggregates. The NBO analysis yields second-order perturbative energy between the H-bond donor and acceptor orbitals correlated with the calculated ionization energies. This sheds light on the role of the oxygen lone-pairs of the uracil CO group in the formation of strong H-bonds, with a stronger directionality in mixed clusters, giving a quantitative explanation for the formation of core–shell structures. [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]

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]

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]

Absolute total cross sections (TCSs) for electron scattering from boron trifluoride (BF3) and phosphorus trifluoride (PF3) molecules have been measured using a linear transmission method. The electron energy ranges from 0.6 to 370 eV for BF3 and from 0.5 to 370 eV for PF3. The TCS energy dependence for BF3 exhibits two very pronounced enhancements: resonantlike narrow feature located near 3.6 eV with the maximum value of 19.2×10-20 m2, and intermediate energy very broad enhancement with two humps, one centered around 21 eV (18.8×10-20 m2 in the maximum) and the other near 45 eV (19.5×10-20 m2). For PF3 the TCS has quite different low-energy dependence: at 0.5 eV it has a high value of 70×10-20 m2 and decreases steeply towards higher energies. Beyond the minimum near 5.5 eV, the TCS reveals two distinct humps: the resonant one centered near 11 eV with the peak value of 32.9×10-20 m2 and the second one much broader around 35 eV (27.9×10-20 m2). The present TCSs for trifluorides are compared to each other as well as to previous TCS data for selected perfluorides and to results for their perhydrided counterparts. The differences and similarities in the shape and magnitude of TCSs are pointed out. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Astrophysical ices are exposed to different radiation fields including photons, electrons and ions. The latter stem from interstellar cosmic rays (CR), the solar and stellar winds, shock waves or are trapped in the magnetospheres of giant planets. We briefly discuss the physics of energy deposition by ion ir radiation in condensed matter and experimental methods to study the induced effects. We then present results on radiation effects such as sputtering, amorphisation and compaction, dissociation of molecules, formation of new molecular species after radiolysis and by implantation of ions. The formation and radio-resistance of organic molecules, related to the question of the initial conditions for the emergence of life, are briefly discussed. This review is not meant to be comprehensive, but rather focusses on recent findings, with special emphasis on experiments with heavy multiply charged ion beams. These experiments aim in particular at simulating the effects of CRs on icy grains in dense molecular clouds, and on the formation of molecules on icy bodies in the Solar System. [ABSTRACT FROM AUTHOR]

This article investigates the radiolysis of a mixture of nitric acid with water (HNO3:H2O) at 16 K in high-vacuum (residual pressure < 10−6 mbar). A nitric acid-water ice film was exposed to 40 MeV 58Ni11+ ion beam in a heavy ion accelerator facility in France. For this astrochemically- and atmospherically-relevant ice mixture of nitric acid and water, we analyze the possible formation and destruction processes of N–O bearing species, thus providing spectroscopic data in the infrared (IR) region for theoretical, laboratory and observational future studies. The irradiation synthetized 18 species which were posteriorly examined by infrared spectroscopy: N2O, NH3, NO, NO2 and H x N y O z molecules, such as hidroxylamine (NH2OH), nitrous acid (HONO) as well as other species with bonding N–O, N–H and H–O–N converting surface-adsorbed nitrogen oxides into astrochemically active NO x. The interaction of HNO3 and H2O originates H–N–O molecular complexes, which were investigated as particular cases of the hydrogen-bonded species formed by a more electronegative atom (N or O) interacts intra or intermolecularly with a donor atom (N or O) and observed in the interstellar medium with higher quantities or great abundances. The HNO3 and H2O destruction cross sections have been determined to be 8.5 × 10−13 and 1.2 × 10−13 cm2, respectively, for the mentioned experimental conditions. [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]

The absolute total cross section (TCS) for electron-ethylene oxide (c-C2H4O) collisions was measured at electron-impact energies extending from 0.7 to 400 eV using the linear electron-transmission technique. In the present TCS energy function a distinct peak is visible near 4.6 eV which may be attributed to formation of a short-lived negative ion. Moreover, at intermediate and high energies the integral elastic (ECS) and ionization (ICS) cross sections were determined numerically. The calculated sum, ECS + ICS, is in good agreement with the experimental TCS in the overlapping energy range. Finally, the present experimental TCS for electron scattering from c-C2H4O is compared with that for its cyclic isoelectronic counterpart c-C3H6, and similarities and differences are pointed out and discussed. [ABSTRACT FROM AUTHOR]

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]

The emergence of the new SARS-CoV-2 virus two years ago strongly affected economic life and labour markets around the world. The pandemic affected many sectors, including the mining industry. Coal companies have had to cope with the challenges and adapt their operations to the situation. Due to the peculiarities of the mines, not only to the hazardous factors and conditions prevailing underground but also to the large number of employees who usually move in groups in the plants, the emergence of a new threat caused by a biological agent posed a real challenge for them. The aim of this paper was to present the initiatives and measures taken in the coal mining sector to ensure the safety of workers during a pandemic. The guidelines for the operation of mining plants during the SARS-CoV-2 epidemic were analysed, as well as the identification of locations in mining plants particularly vulnerable to infection with the virus. We also presented how the pandemic period affected the operations of a selected coal company in Poland from an economic point of view. [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]

Highlights: [•] New experimental results on the implantation of S q+ (q =7, 9, 11) ions (35 and 176keV) in water ice at 80K are presented. [•] The results indicate that implantation produces hydrated sulfuric acid with yields that increase with ion energy. [•] No evidences for the production of SO2 and H2S have been found. [•] Sulfur ion implantation is the dominant formation mechanism of hydrated sulfuric acid at Europa. [Copyright &y& Elsevier]

Many solar system objects, such as planets and their satellites, dust grains in rings, and comets, are known to either be made of ices or to have icy surfaces. These ices are exposed to ionizing radiation including keV, MeV and GeV ions from solar wind or cosmic rays. Moreover, icy dust grains are present in interstellar space and, in particular, in dense molecular clouds. Radiation effects include radiolysis (the destruction of molecules leading to formation of radicals), the formation of new molecules following radiolysis, the desorption or sputtering of atoms or molecules from the surface, compaction of porous ices, and phase changes. This review discusses the application of infrared spectroscopy FTIR to study the evolution of the chemical composition of ices containing the most abundant molecular species found in the solar system and interstellar medium, such as H2O, CO, CO2 and hydrocarbons. We focus on the evolution of chemical composition with ion fluence in order to deduce the corresponding destruction and formation cross sections. Although initial approach focused on product identification, it became increasingly necessary to work toward a comprehensive understanding of ice chemistry. The abundances of these molecules in different phases of ice mantles provide important clues to the chemical processes in dense interstellar clouds, and therefore it is of importance to accurately measure the quantities such as dissociation and formation cross sections of the infrared features of these molecules. We also are able to obtain the scaling of these cross sections with deposited energy. [ABSTRACT FROM AUTHOR]

Abstract: Electron-induced decarboxylation in condensed films of formic acid HCOOH, partially deuterated acetic acid CH3COOD and trifluoroacetic acid CF3COOH, has been studied in the energy range 0.7–20eV by high resolution electron energy loss spectroscopy (HREELS). The yield of carbon dioxide formation shows a peak around 1eV irradiation energy associated with a resonant mechanism involving the transient negative ion [RCOOH]#− and an essentially non-resonant contribution increasing with irradiation energy above an onset located in the range 6–9eV, depending on the carboxylic acid under consideration. The remarkable point of this study is that it is possible to selectively control the decarboxylation reaction by tuning the electron energy of irradiation. [Copyright &y& Elsevier]

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]

We have investigated the effectiveness of molecular hydrogen (H2) formation from Polycyclic Aromatic Hydrocarbons (PAHs) which are internally heated by collisions with keV ions. The present and earlier experimental results are analyzed in view of molecular structure calculations and a simple collision model. We estimate that H2 formation becomes important for internal PAH temperatures exceeding about 2200 K, regardless of the PAH size and the excitation agent. This suggests that keV ions may effectively induce such reactions, while they are unlikely due to, e.g., absorption of single photons with energies below the Lyman limit. The present analysis also suggests that H2 emission is correlated with multi-fragmentation processes, which means that the [PAH-2H]+ peak intensities in the mass spectra may not be used for estimating H2-formation rates. [ABSTRACT FROM AUTHOR]

We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH+) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH+ + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C6H5). Thus nonstatistical fragmentation may be an effective initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures. [ABSTRACT FROM AUTHOR]

We irradiated the complex organic molecule pyridine and mixtures of pyridine and water in the solid phase (thin icy films) at 12 K at different beam lines of the GANIL facility (ARIBE: 90 keV O 6 + , SME: 650 MeV Zn 26 + ) . The destruction of the initial molecule and the appearance of radiolytic products were followed by in-situ infrared absorption spectroscopy as a function of the projectile fluence with the CASIMIR experimental set-up of CIMAP. We measured the destruction cross section as a function of pyridine concentration. A clear dependence on the percentage of pyridine in H 2 O was found: the destruction cross sections are significantly higher for small concentration, i.e. pure pyridine is more radioresistant than pyridine diluted in water ice at 12 K. Thus, the presence of water environment significantly modifies the radiation resistance of the initial complex organic molecules: it enhances radiosensitivity and destruction of pyridine, with implications for radiobiology and astrochemistry. [ABSTRACT FROM AUTHOR]

Several nitrogen-containing molecules have been unambiguously identified in the Solar System and in the Interstellar Medium. It is believed that such a rich inventory of species is a result of the energetic processing of astrophysical ices during the interaction with ionizing radiation. An intrinsic parameter of matter, the complex refractive index, stores all the "chemical memory" triggered by energetic processing, and therefore might be used to probe ice observations in the infrared. In this study, four N-containing ices have been condensed in an ultra-high vacuum chamber and processed by heavy ions (O and Ni) with energies between 0.2 and 15.7 MeV at the Grand Accélérateur National d'Ions Lourds (GANIL), in Caen, France. All chemical changes were monitored in situ by Infrared Absorption Spectroscopy. The complex refractive index was calculated directly from the absorbance spectrum, by using the Lambert-Beer and Kramers-Kroning relations, and the values are available in an online database: https://www..univap.br/gaa/nkabs-database/data.htm. As a result, other than the database, it was observed that non-polar ices are more destroyed by sputtering than polar ones. Such destruction and chemical evolution lead to variation in the IR albedo of samples addressed in this paper. Unlabelled Image • Complex refractive index is key parameter in radiative transfer models of dusty media. • The dataset provided in this paper reduces the lack of data for the astrochemical community. • In general, the refractive index modification triggered by cosmic-ray bombardment, leads to an albedo decreasing in the infrared. [ABSTRACT FROM AUTHOR]

We report on measurements of the ionization and fragmentation of polycyclic aromatic hydrocarbon (PAH) targets in Xe20 + + C16H10 and Xe20 + + [C16H10]k collisions and compare results for the two C16H10 isomers: pyrene and fluoranthene. For both types of targets, i.e., for single PAH molecules isolated in vacuum or for isomerically pure clusters of one of the molecules, the resulting fragment spectra are surprisingly similar. However, we do observe weak but significant isomer effects. Although these are manifested in very different ways for the monomer and cluster targets, they both have at their roots small differences (<2.5 eV) between the total binding energies of neutral, and singly and multiply charged pyrene and fluoranthene monomers. The results will be discussed in view of the density functional theory calculations of ionization and dissociation energies for fluoranthene and pyrene. A simple classical over-the-barrier model is used to estimate cross sections for single- and multiple-electron transfer between PAHs and ions. Calculated single and multiple ionization energies, and the corresponding model PAH ionization cross sections, are given. [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]

Ices are omnipresent in cold regions in space on, e.g., comets, dust grains, transneptunian objects, surfaces of planets and their satellites. The dominant molecule in such ices is water, but also other small molecules or even complex organic molecules (COMs) may be present. Ionizing radiation (UV photons, electrons, ions from cosmic rays or solar wind) induces several physico-chemical processes such as radiolysis. The fragmentation of initial molecules followed by chemical reactions between radicals may lead to formation of new molecules. Furthermore, also implanted projectiles can contribute to chemistry by forming new molecular species. Other observed effects include structural changes (compaction, amorphization) and desorption (sputtering) of particles from the surface. At CIMAP (Caen, France), using the different beam lines of the GANIL facility, and at GSI (Darmstadt, Germany), the interaction of swift highly charged heavy ions with astrophysical ices has been studied in a wide projectile energy range from keV to GeV. Here, two examples of our studies on astrophysical and astrochemical applications will be discussed in detail: 1) the synthesis of COMs under irradiation of ices made of small molecules, and 2) radiosensitivity of COMs such as pyridine, glycine and adenine, both for isolated molecules in the gas phase and in condensed phase. Special emphasis is given on pyridine and pyridine in water matrix. [ABSTRACT FROM AUTHOR]

Abstract: The interaction of 3 keV Ar+ ions with clusters of two structural isomers of C16H10 polycyclic aromatic hydrocarbons, namely fluoranthene and pyrene, has been studied. Following the collision with the atomic projectile, a rich molecular growth inside of the cluster is observed for both isomers. The observed growth processes include the hydrogenation of the parent molecule and the addition of CHx units. They are more important in the case of collisions with fluoranthene clusters, this can be explained by a more flexible carbon skeleton and lower reaction barriers. Moreover, the evolution of the hydrogenation with the size of the growth products gives information on the growth mechanisms. Graphical abstract: [ABSTRACT FROM AUTHOR]

In the present paper, we describe a new home-built crossed-beam apparatus devoted to ion-induced ionization and fragmentation of isolated biologically relevant molecular systems. The biomolecular ions are produced by an electrospray ionization source, mass-over-charge selected, accumulated in a 3D ion trap, and then guided to the extraction region of an orthogonal time-of-flight mass spectrometer. Here, the target molecular ions interact with a keV atomic ion beam produced by an electron cyclotron resonance ion source. Cationic products from the collision are detected on a position sensitive detector and analyzed by time-of-flight mass spectrometry. A detailed description of the operation of the setup is given, and early results from irradiation of a protonated pentapeptide (leucine-enkephalin) by a 7 keV He+ ion beam are presented as a proof-of-principle. [ABSTRACT FROM AUTHOR]

In the present paper, we describe a new home-built crossed-beam apparatus devoted to ion-induced ionization and fragmentation of isolated biologically relevant molecular systems. The biomolecular ions are produced by an electrospray ionization source, mass-over-charge selected, accumulated in a 3D ion trap, and then guided to the extraction region of an orthogonal time-of-flight mass spectrometer. Here, the target molecular ions interact with a keV atomic ion beam produced by an electron cyclotron resonance ion source. Cationic products from the collision are detected on a position sensitive detector and analyzed by time-of-flight mass spectrometry. A detailed description of the operation of the setup is given, and early results from irradiation of a protonated pentapeptide (leucine-enkephalin) by a 7 keV He+ ion beam are presented as a proof-of-principle. [ABSTRACT FROM AUTHOR]

We show that the energetic processing of C 60 clusters by slow atomic projectiles leads to ultrafast ( < ps ) formation of large covalent carbon nanoparticles containing a few hundreds of atoms. The underlying mechanism is found to be due to impulse-driven collisions between the projectile and the nuclei of the molecules. Experimental findings are well reproduced by classical molecular dynamics simulations. The cross sections for molecular growth processes forming covalent systems which contain more than 60 carbon atoms are about 5 ⋅ 10 − 14 cm 2 representing more than 70% of the geometrical cross sections. This demonstrates the high efficiency of the underlying processes. The formed carbon nanoparticles contain both aromatic and aliphatic structures which have also been considered as dust components in space. [ABSTRACT FROM AUTHOR]

Silicates are the dominant surface material of many Solar System objects, which are exposed to ion bombardment by solar wind ions and cosmic rays. Induced physico-chemical processes include sputtering which can contribute to the formation of an exosphere. We have measured sputtering yields and velocity spectra of secondary ions ejected from nepheline, an aluminosilicate thought to be a good analogue for Mercury's surface, as a laboratory approach to understand the evolution of silicate surfaces and the presence of Na and K vapor in the exosphere. Experiments were performed with highly charged ion beams (keV/u–MeV/u) delivered by GANIL using an imaging XY-TOF-SIMS device under UHV conditions. The fluence dependence of sputtering yields gives information about the evolution of surface stoichiometry during irradiation. From the energy distributions N(E) of sputtered particles, the fraction of particles which could escape from the gravitational field of Mercury, and of those falling back and possibly contributing to populate the exosphere can be roughly estimated. [ABSTRACT FROM AUTHOR]

The presence of nucleobases in carbonaceous meteorites on Earth is an indication of the existence of this class of molecules in outer space. However, space is permeated by ionizing radiation, which can have damaging effects on these molecules. Adenine is a purine nucleobase that amalgamates important biomolecules such as DNA, RNA, and ATP. Adenine has a unique importance in biochemistry and therefore life. The aim of this work was to study the effects of cosmic ray analogues on solid adenine and estimate its survival when exposed to corpuscular radiation. Adenine films were irradiated at GANIL (Caen, France) and GSI (Darmstadt, Germany) by 820 MeV Kr33+, 190 MeV Ca10+, 92 MeV Xe23+, and 12 MeV C4+ ion beams at low temperature. The evolution of adenine molecules under heavy ion irradiation was studied by IR absorption spectroscopy as a function of projectile fluence. It was found that the adenine destruction cross section ( σd) follows an electronic stopping power ( Se) power law under the form: CSe n; C is a constant, and the exponential n is a dimensionless quantity. Using the equation above to fit our results, we determined σd = 4 × 10−17 Se1.17, with Se in kiloelectronvolts per micrometer (keV μm−1). New IR absorption bands arise under irradiation of adenine and can be attributed to HCN, CN-, C2H4N4, CH3CN, and (CH3)3CNC. These findings may help to understand the stability and chemistry related to complex organic molecules in space. The half-life of solid adenine exposed to the simulated interstellar medium cosmic ray flux was estimated as (10 ± 8) × 106 years. Key Words: Heavy ions-Infrared spectroscopy-Astrochemistry-Cosmic rays-Nucleobases-Adenine. Astrobiology 17, 298-308. [ABSTRACT FROM AUTHOR]

We present new experimental results relative to 144 keV S 9 + or Ar 9 + ion implantation in targets made of oxygen rich frozen gases (O 2 , CO 2 ) and mixtures with water ice. Spectra in the UV (200–400 nm) range have been obtained before and after implantation. The targets have been selected because they can be representative of the parent molecules from which SO 2 and O 3 , observed to be present on the surfaces of Jupiter’s icy Moons, could be formed due to radiolysis induced by the abundant magnetospheric ions. The results indicate that sulfur dioxide is not detectable after sulfur implantation in oxygen bearing species. Ozone is formed after argon and sulfur ion implantation. Sulfur implantation in O 2 and CO 2 targets also induces the formation of a band centered at about 255 nm (that we tentatively attribute to SO 3 − radicals). In the mixtures with water the band appears initially at the same wavelength and shifts to about 247 nm at higher ion fluences possibly indicating the formation of sulfite (HSO 3 − ) ions. An absorption band observed on Ganymede is well fitted by using three components: ozone, sulfite ions and a not identified component having an absorption band centered at 298 nm. In all of the studied cases ion implantation produces a spectral reddening over the investigated spectral range (200–400 nm) that well mimics the observed spectral slopes of Jupiter’s icy satellites. [ABSTRACT FROM AUTHOR]

Solid carbon dioxide (CO 2 ) is found in several bodies of the solar system, the interstellar medium (ISM) and young stellar objects, where it is exposed to cosmic and stellar wind radiation. Here, the chemical and physical modifications induced by heavy ion irradiation of pure solid CO 2 at low temperature ( T = 15–30 K) are analyzed. The experiments were performed with Ti (550 MeV) and Xe (630 MeV) ions at the UNILAC of GSI/Darmstadt and with Ni ions (46 and 52 MeV) at IRRSUD of GANIL/Caen. The evolution of the thin CO 2 ice films (deposited on a CsI window) was monitored by mid-infrared absorption spectroscopy (FTIR). The dissociation rate of CO 2 , determined from the fluence dependence of the IR absorption peak intensity, is found to be proportional to the electronic stopping power S e . We also confirm that the sputtering yield shows a quadric increase with electronic stopping power. Furthermore, the production rates of daughter molecules such as CO, CO 3 and O 3 were found to be linear in S e . [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]

Wepresent a combined experimental and theoretical study of theionization of N-acetylglycine molecules by 48 keVO6+ions. We focus on the single ionization channel ofthis interaction. In addition to the prompt fragmentation of the N-acetylglycine cation, we also observe the formation ofmetastable parent ions with lifetimes in the microsecond range. Onthe basis of density functional theory calculations, we assign thesemetastable ions to the diol tautomer of N-acetylglycine.In comparison with the simple amino acids, the tautomerization rateis higher because of the presence of the peptide bond. The study ofa simple biologically relevant molecule containing a peptide bondallows us to demonstrate how increasing the complexity of the structureinfluences the behavior of the ionized molecule. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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]

Highlights: [•] We compare statistical and non-statistical fragmentation of fullerenes and PAHs. [•] Non-statistical fragmentation is important in ∼100eV PAH-He collisions. [•] Non-statistical fragmentation gives highly reactive fragments. [Copyright &y& Elsevier]