Destruction Cross Sections Research Articles

Formation of N–bearing complex organic molecules in molecular clouds: Ketenimine, acetonitrile, acetaldimine, and vinylamine via the UV photolysis of C2H2 ice

Context. The solid-state C2H2 chemistry in interstellar H2O-rich ice has been proposed to explain astronomically observed complex organic molecules (COMs), including ketene (CH2CO), acetaldehyde (CH3CHO), and ethanol (CH3CH2OH), toward early star-forming regions. This formation mechanism is supported by recent laboratory studies and theoretical calculations for the reactions of C2H2+OH/H. However, the analog reaction of C2H2+NH2 forming N-bearing species has been suggested to have a relatively low rate constant that is orders of magnitude lower than the value of C2H2+OH. Aims. This work extends our previous laboratory studies on O-bearing COM formation to investigate the interactions between C2H2 and NH3 ice triggered by cosmic ray-induced secondary UV photons under molecular cloud conditions. Methods. Experiments were performed in an ultra-high vacuum chamber to investigate the UV photolysis of the C2H2:NH3 ice mixture at 10 K. The ongoing chemistry was monitored in situ by Fourier-transform infrared spectroscopy as a function of photon fluence. The IR spectral identification of the newly formed N-bearing products was further secured by a quadrupole mass spectrometer during the temperature-programmed desorption experiment. Results. The studied ice chemistry of C2 H2 with NH2 radicals and H atoms resulting from the UV photodissociation of NH3 leads to the formation of several N-bearing COMs, including vinylamine (CH2CHNH2), acetaldimine (CH3CHNH), acetonitrile (CH3CN), ketenimine (CH2CNH), and tentatively ethylamine (CH3CH2NH2). The experimental results show an immediate and abundant CH2CHNH2 yield as the first-generation product, which is further converted into other chemical derivatives. The effective destruction and formation cross-section values of parent species and COMs were derived, and we discuss the chemical links among these molecules and their astronomical relevance.

Experimental study on the radiation-induced destruction of organic compounds on the surface of the Moon

Volatile organic molecules and a complex organic refractory material were detected on the Moon and on lunar samples. The Moon’s surface is exposed to a continuous flux of solar UV photons and fast ions, e.g. galactic cosmic rays (GCRs), solar wind (SW), and solar energetic particles (SEPs), that modify the physical and chemical properties of surface materials, thus challenging the survival of organic compounds. With this in mind, the aim of this work is to estimate the lifetime of organic compounds on the Moon’s surface under processing by energetic particles. We performed laboratory experiments to measure the destruction cross section of selected organic compounds, namely methane (CH4), formamide (NH2CHO), and an organic refractory residue, under simulated Moon conditions. Volatile species were deposited at low temperature (17 - 18 K) and irradiated with energetic ions (200 keV) in an ultra-high vacuum chamber. The organic refractory residue was produced after warming up of a CO:CH4 ice mixture irradiated with 200 keV H+ at 18 K. All the samples were analyzed in situ by infrared transmission spectroscopy. We found that destruction cross sections are strongly affected (up to one order of magnitude) by the dilution of a given organic in an inert matrix. Among the selected samples, organic refractory residues are the most resistant to radiation. We estimated the lifetime of organic compounds on the surface of the Moon by calculating the dose rate due to GCRs and SEPs at the Moon’s orbit and by using the experimental cross section values. Taking into account impact gardening, we also estimated the fraction of surviving organic material as a function of depth. Our results are compatible with the detection of CH4 in the LCROSS eject plume originating from layers deeper than about 0.7 m at the Moon’s South Pole and with the identification of complex organic material in lunar samples collected by Apollo 17 mission.

EXPERIMENTAL SIMULATION OF FAST ELECTRON BOMBARDMENT OF METHANOL ICE AND ITS IMPLICATIONS IN ASTROCHEMISTRY

In this work, we experimentally simulate the methanol (CH3OH) ice behavior (12 K) through the bombarded by fast electrons (4.9 keV) in an attempt to simulate radiation chemistry induced by radiation in space environments. The sample analysis by infrared spectroscopy reveals the appearance of new species, including CO2, CO, H2O, and CH4, during the sample bombardment. We have quantified the effective destruction cross-section of methanol (5.5 × 10-19 cm2) and determined the formation cross-section for these newly produced species. Additionally, we have characterized the chemical equilibrium (CE) phase, which becomes evident at higher fluences. We have also calculated molecular abundances and assessed the desorption yield induced by fast electrons within the same sample. Furthermore, we estimated the timescale required to achieve chemical equilibrium in specific astrophysical environments impacted by electrons. This study significantly contributes to our comprehension of electron bombardment behavior in astrophysical ices and allows for meaningful comparisons with organic-rich ices in space environments

Formation of N–O–H bearing species in HNO3 and H2O icy samples by heavy-ion irradiation: an infrared spectroscopic study

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.

LABORATORY INVESTIGATION OF X-RAY PHOTOLYSIS OF ETHANOL ICE AND ITS IMPLICATION ON ASTROPHYSICAL ENVIRONMENTS

Here we present experimental results on the irradiation of ethanol ice (CH3CH2OH) by broadband soft X-rays to simulate the effect processing of organic-rich astrophysical ices by space radiation. This molecule was detected in the interstellar medium in molecular clouds like Sagittarius B2 and towards nebulas like Orion KL. The experiments were performed at the Brazilian Synchrotron Facility LNLS/CNPEM, at Campinas, SP. The frozen sample was analyzed in-situ by infrared spectroscopy (IR) in a simulated astrophysical environment at different radiation fluences. The results show the formation of several new molecular species such as CO2, CO, H2O, CH4, CH3(CO)CH3 (acetone), and CH3COOH (acetic acid). We determined the effective destruction cross-section of ethanol (~1×10-18 cm2) and the formation cross-sections of the daughter species with values between 0.5 to 3.4×10-18 cm2. The chemical equilibrium phase of ice was characterized and desorption yield induced by X-rays was determined (0.13 molecules photon-1). The result helps us to understand the photolysis induced by X-rays in organic-rich ices in space environments.

Bombardment of CO Ice by Cosmic Rays. I. Experimental Insights into the Microphysics of Molecule Destruction and Sputtering

We present a dedicated experimental study of microscopic mechanisms controlling radiolysis and sputtering of astrophysical ices upon bombardment by cosmic-ray ions. Such ions are slowed down owing to inelastic collisions with bound electrons, resulting in ionization and excitation of ice molecules. In experiments on CO ice irradiation, we show that the relative contribution of these two mechanisms of energy loss to molecule destruction and sputtering can be probed by selecting ion energies near the peak of the electronic stopping power. We have observed a significant asymmetry, in both the destruction cross section and the sputtering yield, for pairs of ion energies corresponding to the same values of the stopping power on either side of the peak. This implies that the stopping power does not solely control these processes, as usually assumed in the literature. Our results suggest that electronic excitations represent a significantly more efficient channel for radiolysis and, likely, for sputtering of CO ice. We also show that the charge state of incident ions and the rate for CO+ production in the ice have a negligible effect on these processes.

Swift heavy ion irradiation of thymine at cryogenic temperature

Thymine (C5H6N2O2) 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 Se as σ=Se/D0, where D0=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.

Stability of urea in astrophysical ices. A laboratory study of VUV irradiation and high-energy electron bombardment

ABSTRACT The recent detection of urea in the interstellar medium raises questions about its stability in different astronomical environments. In this work, we have studied the stability of urea ices and urea/water ice mixtures under vacuum-ultraviolet (VUV; 6.3–10.9 eV) irradiation and high-energy (5 keV) electron bombardment at 30, 100, and 200 K. The evolution of the ices was monitored with infrared spectroscopy. CO2, HNCO, and OCN− were identified as reaction products in the 30 K samples. At the higher temperatures CO2 and HNCO were hardly found in the processed ices. The measurements provided destruction cross-sections and allowed the derivation of radiation yields, G100, and half-life doses for urea. G100 values were found to be low (≈3.6–0.3 molecules/100 eV) both for VUV photons and high-energy electrons with electrons being slightly more efficient for the destruction of the molecule. These low G100 values are likely due to favourable mechanisms of energy dissipation or urea recombination. The stability of urea under irradiation increases with temperature which suggests that higher mobility improves the repair mechanisms. Estimates based on these laboratory data indicate that urea should be stable (≈108–109 yr) against irradiation in cold dense clouds and hot cores. It would not survive long (≈103–104 yr) on the bare surface of a Kuiper belt object, but would be well protected (≈109 yr) against radiation below a 30 $\mu$m ice layer. The high resistance of the molecule to radiation damage makes it a good candidate for prebiotic chemistry.

Model on degradation of thick solid molecular targets by energetic ion and electron beams

Thick targets are those inside which incoming projectiles lose all or most of their kinetic energy. One of the main characteristics of these systems is the highly inhomogeneous degradation of molecular samples as a function of depth; as a consequence, the molecular destruction rate during irradiation differs substantially from the expected exponential decrease. The proposed model predicts the profile of the molecular damage as function of depth in the target as well as the evolution of the molecular column density as a function of beam fluence. Codes, such as TRIM and CASINO, are used to extract collisional information on the projectile-solid interaction which, in turn, is used to determine the dependence of destruction cross sections on depth. Theoretical predictions are presented. Comparisons with experimental data are referenced.

Desorption of polycyclic aromatic hydrocarbons by cosmic rays

Context. The rate of sputtering and release of condensed species is an important aspect of interstellar chemistry, as is photodesorption for the most volatile species, because in the absence of such mechanisms the whole gas phase would have to condense in times often shorter than the lifetime of the considered medium, in particular for dense clouds. The recent detection of cyclic aromatic molecules by radioastronomy requires an understanding of the potential mechanisms supporting the rather high abundances observed. Aims. We perform experiments to advance our understanding of the sputtering yield due to cosmic rays for very large carbonaceous species in the solid phase. Methods. Thin films of perylene and coronene were deposited on a quartz cell microbalance and exposed to a 1.5 MeV N+ ion beam at the Laboratoire de Physique des 2 Infinis Irène Joliot-Curie (IJCLab, Orsay, France) and a 230 MeV 48Ca10+ ion beam at the GSI Helmholtzzentrum für Schwerionenforschung (GSI, Darmstadt, Germany). The mass loss was recorded as a function of the fluence for the N+ beam. The microbalance response was calibrated using Fourier transform infrared (FTIR) reflectance measurements of the produced films. In addition, the destruction cross-section of the same species was measured with the 48Ca10+ ion beam by in situ monitoring of the evolution of the infrared spectra of the bombarded films. Results. We deduced the sputtering yield for perylene and coronene and their radiolysis destruction cross-sections. Combining these results with a cosmic ray astrophysical spectrum, we discuss the impact on the possible abundance that may originate from the sputtering of dust grains with these molecules as well as from polycyclic aromatic molecules when they are trapped in ice mantles.

Swift heavy ions irradiation of water ice at different temperatures: hydrogen peroxide and ozone synthesis and sputtering yield

ABSTRACT Water ices at 15 and 144 K were bombarded by swift heavy ions, 45.8 MeV 58Ni11 + and 606 MeV 64Zn26 +, to measure the induced chemical and physical effects. The column densities of water and the synthesized species, hydrogen peroxide (H2O2) and ozone (O3), were monitored via infrared spectroscopy. The formation and destruction cross-sections of precursor and products were determined and compared with literature. The H2O2 formation and destruction cross-sections reveal a linear dependence with electronic stopping power, σ ∝ Se. The sputtering yield (Y0) shows a power law with electronic energy lost, $Y_0\propto S_\mathrm{e}^2$, and an exponential increase with the sample temperature. The findings indicate that the radiolysis rate of water ice is higher at low temperatures while the desorption yield increases at higher temperatures. A large amount of water ice is located in the grain mantles of the circumstellar envelopes and the interstellar medium regions, which are exposed to galactic cosmic rays (GCRs). The synthesis of H2O2 and O3 molecules as a function of absorbed doses of GCR irradiation and their irradiation time is analysed in detail. Besides, the extrapolation of the sputtering yield rates, as a function of time and temperature, for astrophysical conditions can contribute to a better understanding of non-thermal sputtering of water ices.

Lyα irradiation of solid-state formamide

Context. Formamide (NH2CHO) has been proposed as a potential prebiotic precursor in the scientific discourse on the origin of life. It has been observed in different environments in space, including protostellar regions and comets. The abundance and stability of NH2CHO in the early stages of star formation can be better understood by incorporating the formation and destruction data in astrochemical models. Aims. We carried out an experimental investigation to study the destruction of pure NH2CHO ice at 12 K as a result of the interaction with Lyα (121.6 nm) photons. Methods. We studied UV photo destruction of NH2CHO using Fourier-transform infrared spectroscopy. Results. After UV processing, the intensity of NH2CHO IR bands decreased and new bands corresponding to HCN, CO, NH4+ OCN−, HNCO, and CO2 appeared in the spectrum. We then derived the destruction and cumulative product formation cross-sections. Conclusions. A comparison of destruction rates derived from the cross-section in a cold and dense molecular cloud for different energetic processing agents reveals that UV photons induce NH2CHO destruction at a level that is one order of magnitude greater than that affected by cosmic rays; however, it is three orders of magnitude lower than that of H atoms.

Irradiation of Phenylalanine at 300 K by MeV Ions.

Phenylalanine (Phe) is an amino acid that has been identified in carbonaceous meteorites; its formation mechanism in space is unknown, and its radioresistance has been the subject of investigation. This work aims at studying, in the laboratory, the Phe radiolysis by cosmic analogues. The Phe destruction rate, at 300 K, is measured for H, He, and N ion beam irradiation in the 0.5 to 2 kinetic MeV range. Fourier transform infrared (FTIR) spectroscopy was employed to monitor the molecular degradation as a function of fluence. The Phe apparent destruction cross-section, σapd, which includes radiolysis and sputtering processes, is determined to be proportional to the electronic stopping power, Se. The measured parameter D0 = 14.3 ± 2.2 eV/molec in the relationship, and = Se/D0 is interpreted as the mean absorbed dose necessary to dissociate or eject a Phe molecule. The Phe half-life in the interstellar medium is predicted to be about 10 million years, H+ ions the main destructive cosmic ray constituent.

Chemical reactions in H2O:CO interstellar ice analogues promoted by energetic heavy-ion irradiation

ABSTRACT 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.

On the synthesis of N–O bearing species in astrophysical ices – an infrared spectroscopic study using heavy-ion irradiation of solid N2:CO samples

ABSTRACT 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.

Infrared analysis of Valine degradation by keV electrons. Measurements and CASINO-extended model predictions

ABSTRACTDegradation of L-valine by 0.06–1.0-keV electron beams is analysed in laboratory, at 10, 150, and 300 K. Valine film thicknesses are measured by profilometry, permitting band strength determination for selected valine bands. The column density evolutions during the irradiation are measured via infrared spectroscopy and destruction cross-sections are extracted; the latter range from 1–100 × 10−16 cm2. Data show that, in general, destruction cross-sections depend not only on projectile energy and sample temperature but also on sample thickness and beam fluence. In order to understand these findings, a statistical model is proposed for describing the radiolysis of organic materials. Comparing predictions with experimental results for valine, the main trends are reproduced. The quantitative disagreement indicates that it is necessary to include sputtering in the model. A major contribution of the model is to permit to simulate, layer by layer, the sample degradation rate as a function of fluence. The model assumes that the destruction cross-section of precursor molecules is proportional to the local stopping power and uses the Monte Carlo CASINO code to determine the deposited energy distribution in the bulk. As astrophysical implications, the radiolysis of valine dissolved in H2O ice and shielded by a CO2 layer is predicted, as an attempt to analyse the degradation of realistic cosmic materials by keV electrons.

2-aminooxazole in Astrophysical Environments: IR Spectra and Destruction Cross Sections for Energetic Processing

Abstract 2-aminooxazole (2AO), a N-heterocyclic molecule, has been proposed as an intermediate in prebiotic syntheses. It has been demonstrated that it can be synthesized from small molecules such as cyanamide and glycoaldehyde, which are present in interstellar space. The aim of this work is to provide infrared (IR) spectra, in the solid phase for conditions typical of astrophysical environments and to estimate its stability toward UV photons and cosmic rays. IR (4000–600 cm−1) absorption spectra at 20 K, 180 K, and 300 K, IR band strengths, and room-temperature UV (120–250 nm) absorption spectra are given for the first time for this species. Destruction cross sections of ≈9.5 10−18 cm2 and ≈2 10−16 cm2 were found in the irradiation at 20 K of pure 2AO and 2AO:H2O ices with UV (6.3–10.9 eV) photons or 5 keV electrons, respectively. These data were used to estimate half-life times for the molecule in different environments. It is estimated that 2AO could survive UV radiation and cosmic rays in the ice mantles of dense clouds beyond cloud collapse. In contrast, it would be very unstable on the surface of cold solar system bodies like Kuiper Belt objects, but the molecule could still survive within dust grain agglomerates or cometesimals.

Radiolysis of pyridine in solid water

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 $$\hbox {O}^{\mathrm {6+}}$$ , SME: $$650\, \hbox {MeV Zn}^{\mathrm {26+}})$$ . 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 $$\hbox {H}_{\mathrm {2}}\hbox {O}$$ 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.

Infrared analysis of Glycine dissociation by MeV ions and keV electrons

ABSTRACT Knowledge on amino acid’s dissociation rates by solar wind is relevant for the study of biomaterial resistance in space. The radiolysis and sputtering of glycine by 1 keV electron beam and by 1.8 MeV H+, 1.5 MeV He+, and 1.5 MeV N+ ion beams are studied in laboratory at room temperature. Infrared spectroscopy is used to determine column density decrease rates and destruction cross-sections. Present results stand in good agreement with those found in the literature and show that over five orders of magnitude, apparent destruction cross-sections (which includes sputtering), σdap, are approximately proportional to the electronic stopping power, Se, that is σdap ≈ aSe, where 1/a ≈ 120 eV nm−3. This value corresponds to the mean absorbed energy density necessary to dissociate (and/or eject) glycine; if it is taken as the minimum energy for molecular destruction, than the stopping power threshold is 23 keV μm−1. Assuming σdap = aSe for electron and ion projectiles, the half-life of pure α-glycine is estimated for the solar wind processing at 1 au: about 10 D for protons or electrons and 40 D for He ions.

Radiolysis of NH3:CO ice mixtures – implications for Solar system and interstellar ices

ABSTRACT 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 (Se) 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.