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Here, we present calculations on the energy delivered (and heating) by realistic cosmic rays (CRs) field at a typical molecular clump. The current model describes, with unprecedented spatial resolution, the energy delivery by a realistic CR field in molecular clumps. The calculations were performed employing the Geant4 code (considering full cascade physical processes and hadron physics) considering the cosmic ray field taken from the Voyager spacecraft measurements in the interstellar medium. The results showed that the total energy deposition rate, considering light particles (protons, electrons and alphas), medium-mass ions and heavy-ions, ranges from 400 MeV/g/s in the outer layer (at 105 AU) to roughly 100 MeV/g/s in the inner layer of the model (below 0.1 AU). The main energy deposition rate is due to the incoming protons. Incoming alphas represent 15–20 per cent of the energy deposition. In the deep core of the cloud, the fraction of energy delivered by medium-mass ions, electrons, and heavy ions are 5 per cent, 2.5 per cent, and 1 per cent, respectively. The heating induced by cosmic rays seems to affect mostly the regions above ∼500 AU. Considering a balanced heat model with warm dust grains (T∼16–18 K), we observe a small bump in temperature at 2000–5000 AU. We suggest this temperature enhancement by CRs might have some affect on the molecular formation or cometary formation in pristine Oort cloud region inside the Solar System.

In the interstellar medium, Galactic and extragalactic cosmic rays (CRs) penetrate deeper in the molecular clouds (MCs) and promote inside several physical and physicochemical changes due to the energy deposition, including gas and grain heating, and triggering also molecular destruction and formation. In this work, in an attempt to simulate, in a more realistic way, the energy delivered by CRs in a typical MC (mass ∼5400 M☉ and size ∼106 au; mainly composed of H atoms), we combine the energy deposition of light particles and heavy ions, with the new calculations considering the medium-mass ions (3 ≤ Z ≤ 11). To execute the calculation, the Monte Carlo toolkit GEANT4 was applied to get the energy deposition rate per mass from many kinds of secondary particles, used in nuclear and hadron physics. The energy deposition by its induced cascade shower within the MC was characterized, as well as the relative energy deposition for all members of the medium-mass group. The results show that the incoming protons are the dominant source in the energy deposition and heating of the cloud, followed by alphas and electrons, with the medium-mass-ion and heavy-ion groups each contributing roughly 8 per cent. The current model also shows a temperature enhancement of up to 10 per cent in the external layers of the cloud (reaching 22.5 K) with respect to the previous calculations where only light particles were considered. However, neither heavy nor medium-mass ions contribute to the temperature enhancement in the deep core of the cloud.

In this work, we analyse soft X-ray emission due to mass accretion on to compact stars and its effects on the time-scale to reach chemical equilibrium of eventual surrounding astrophysical ices exposed to that radiation. Reaction time-scales due to soft X-ray in water-rich and pure ices of methanol, acetone, acetonitrile, formic acid, and acetic acid were determined. For accretion rates in the range $\dot{m}=10^{-12}\!-\!10^{-8}\,{\rm M}_\odot$ yr−1 and distances in the range 1–3 LY from the central compact objects, the time-scales lie in the range 10–108 yr, with shorter time-scales corresponding to higher accretion rates. Obtained time-scales for ices at snow-line distances can be small when compared to the lifetime (or age) of the compact stars, showing that chemical equilibrium could have been achieved. Time-scales for ices to reach chemical equilibrium depend on X-ray flux and, hence, on accretion rate, which indicates that systems with low accretion rates may not have reached chemical equilibrium.

Astrophysical ices are being exposed to ionizing radiation in space environments, which trigger new reactions and desorption processes. In the lab, such processing by radiation has revealed the appearance of several new species and complements the study of the chemical evolution of icy astrophysical scenarios. Here, we develop a computational methodology that helps to clarify the chemical evolution of ices investigated experimentally under photolysis/radiolysis processes until reaching chemical equilibrium (CE). Briefly, the code (named PROCODA) solves a system of coupled differential equations and describes the evolution of the molecular abundances with the irradiation time for ices under processing by radiation. Two experimental ice samples containing pure CO2 and irradiated by two ionizing agents (cosmic rays and ultraviolet photons) were considered prototype systems. Here, we considered 11 different chemical species within the ice (four observed: CO2, CO, O3, and CO3; seven nonobserved or unknown: O, O2, C, C2, C2O, C2O2, and C2O3), 100 reaction routes (e.g., direct dissociation reactions, bimolecular and termolecular reactions) and radiation-induced desorption processes. The best-fit models provide the reaction rates, several desorption parameters, as well as the characterization of the CE phase. At CE, the percentage of nonobserved species in the UV model was almost triple the one calculated in the CR model (which also includes a lot of O and C atoms). The determined values can be employed in future astrochemical models to map chemical evolution embedded species in astrophysical regions under the presence of an ionizing radiation field.

In this work, broad-band soft X-ray (6–2000 eV) was employed to irradiate frozen acetonitrile CH3CN, at the temperature 13 K, with different photon fluences up to 1.5 × 1018 photons cm–2. Here, ace...

In this study, we employed broadband X-rays ($6-2000$ eV) to irradiate the frozen acetone CH$_3$COCH$_3$, at the temperature of 12 K, with different photon fluences up to $2.7\times 10^{18}$ photons cm$^{-2}$. Here, we consider acetone as a representative complex organic molecule (COM) present on interstellar ice grains. The experiments were conduced at the Brazilian synchrotron facility (LNLS/CNPEN) employing infrared spectroscopy (FTIR) to monitor chemical changes induced by radiation in the ice sample. We determined the effective destruction cross-section of the acetone molecule and the effective formation cross-section for daughter species. Chemical equilibrium, obtained for fluence $2\times 10^{18}$ photons cm$^{-2}$, and molecular abundances at this stage were determined, which also includes the estimates for the abundance of unknown molecules, produced but not detected, in the ice. Timescales for ices, at hypothetical snow line distances, to reach chemical equilibrium around several compact and main-sequence X-ray sources are given. We estimate timescales of 18 days, 3.6 and 1.8 months, $1.4\times 10^9-6\times 10^{11}$ years, 600 and $1.2\times 10^7$ years, and $10^7$ years, for the Sun at 5 AU, for O/B stars at 5 AU, for white dwarfs at 1 LY, for the Crab pulsar at 2.25 LY, for Vela pulsar at 2.25 LY, and for Sagittarius A* at 3 LY, respectively. This study improves our current understanding about radiation effects on the chemistry of frozen material, in particular, focusing for the first time, the effects of X-rays produced by compact objects in their eventual surrounding ices., Comment: Accepted in MNRAS. This is a preprint. 14 pages, 7 figures

The reaction between carbon monoxide and water was studied occurring in an aerosol medium rich in methanol. This environment is plausible for the primitive and prebiotic Earth atmosphere. The chemical environment is expressed in terms of dielectric constant (e) and the chemical system was modeled employing the polarizable continuum model (PCM). The main results were acquired from calculations employing the M06-2X density functional for the electronic structure calculations and the canonical variational theory with small curvature tunneling for the chemical kinetic calculations. The rise of e affects both the thermochemistry and the kinetics of the reaction, increasing the barrier height and decreasing the rate constant for the reaction occurring at room temperature. For example, the rate constant at 300 K is 5–10× 10− 53 cm3 ⋅molecule− 1 ⋅s− 1 for low dielectric constant (e < 3) and around 2–4× 10− 53 cm3 ⋅molecule− 1 ⋅s− 1 for e between 7 and 40. Our results indicate that the e variation allows a fine tuning to the rate of the reaction.

The reaction between carbon monoxide and water was studied occurring in an aerosol medium rich in methanol. This environment is plausible for the primitive and prebiotic Earth atmosphere. The chemical environment is expressed in terms of dielectric constant (ε) and the chemical system was modeled employing the polarizable continuum model (PCM). The main results were acquired from calculations employing the M06-2X density functional for the electronic structure calculations and the canonical variational theory with small curvature tunneling for the chemical kinetic calculations. The rise of ε affects both the thermochemistry and the kinetics of the reaction, increasing the barrier height and decreasing the rate constant for the reaction occurring at room temperature. For example, the rate constant at 300 K is 5-10× 10

International audience; The synthesis of Methylenimine and Cyanomethanimine from ion irradiation of N2-CH4 ice was studied, in an attempt to simulate the role of medium mass cosmic rays and energetic solar particles in the processing of nitrogen-rich ices on cold astrophysical environments, such as those in the outer region of the Solar System (e.g. Pluto, Charon, Triton, Makemake and Titan). The N2-CH4 (90:10) ice mixture was irradiated at 9 K by 38.4 MeV 40 Ca 9+ (0.96 Mev/u) at the GANIL facility (Caen/Fance). The evolution of the samples was monitored using in-situ Fourier transform infrared spectroscopy (FTIR). The results indicate the formation of CH2NH and CH2NCN, which are considered species of interest in prebiotic chemistry. Other species produced by radiolysis were HCN, HNC, hydrocarbons and nitriles. Direct comparison of the laboratory spectrum from the mixture of reaction products provides an efficient way to focus on the identification of chemical synthesis routes for the production of molecules important in the development of life that are consistent with the chemical inventory and physical conditions on frozen moons and cold objects in the outer Solar System.

In this work, we investigate the effects induced by the heating of acetonitrile-rich ice from 13 K to 350 K. Before the heating, the sample was irradiated at 13 K by broadband X-rays (6 eV to 2 keV), which trigger the production of new molecules, such as HCN, H2CCNH, CH4 and CH3NC (see Carvalho and Pilling, 2020) and also induced desorption of frozen species to gas-phase. New spectra were collected during heating to investigate whether new species, not present before at lower temperatures, appear due to thermal processing. New infrared bands were identified at temperatures around 120 K and 300 K, from which it was possible to notice the possible presence of HCN/CN radical, ammonia and C2N2. It was also verified that acetonitrile has a thermal desorption peak between 120 K and 200 K, which yields to the vanishing of acetonitrile within the sample for temperatures of 200 K and above. Some infrared features assigned before solely to acetonitrile remain for sample temperatures > 200 K, which indicates the presence of blended species with similar infrared features. From analyzing those blended peaks, we also perceived the possible presence of aminoacetonitrile.

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

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 Accelerateur 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://www1.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.

The physical evolution of Young Stellar Objects (YSOs) is accompanied by an enrichment of the molecular complexity, mainly triggered by the heating and energetic processing of the astrophysical ices. In this paper, a study of how the ice column density varies across the protostellar evolution has been performed. Tabulated data of H$_2$O, CO$_2$, CH$_3$OH, HCOOH observed by ground- and space-based telescopes toward 27 early-stage YSOs were taken from the literature. The observational data shows that ice column density and spectral index ($\alpha$), used to classify the evolutionary stage, are well correlated. A 2D continuum radiative transfer simulation containing bare and grains covered by ices at different levels of cosmic-ray processing were used to calculate the Spectral Energy Distributions (SEDs) in different angle inclinations between face-on and edge-on configuration. The H$_2$O:CO$_2$ ice mixture was used to address the H$_2$O and CO$_2$ column density variation whereas the CH$_3$OH and HCOOH are a byproduct of the virgin ice after the energetic processing. The simulated spectra were used to calculate the ice column densities of YSOs in an evolutionary sequence. As a result, the models show that the ice column density variation of HCOOH with $\alpha$ can be justified by the envelope dissipation and ice energetic processing. On the other hand, the ice column densities are mostly overestimated in the cases of H$_2$O, CO$_2$ and CH$_3$OH, even though the physical and cosmic-ray processing effects are taken into account., Comment: Accepted for publication in The Astrophysical Journal. 29 pages, 16 figures

The survival of astrophysical ices in the star-forming regions depends on the suitability of temperature, density and radiation conditions. In this paper, the role of Interstellar Radiation Field (ISRF) on ices in Elias 29 is addressed. This object is the most luminous protostar in $\rho$ Oph E molecular cloud, and is surrounded by many Young Stellar Objects distant only a few arcminutes. In addition, other two brightness BV stars (S1 and HD 147889) enhance the external irradiation in Elias 29. This study was carried out by using the Monte Carlo radiative transfer code RADMC-3D assuming an internal and external irradiation. As result, we found that HD 147889 dominates the ISRF, instead of the closest protostars, and contributes to enhance the external irradiation in 44 times the standard value. Furthermore, remarkable effects are observed in FIR spectrum, as well as in near-IR image. Additionally, the snowline positions of volatile compounds, such as CO, O$_2$, N$_2$ and CH$_4$ are redefined to a toroidal-shaped morphology in the envelope, with low FUV flux (10$^{-7}$ ergs cm$^{-2}$ s$^{-1}$). In such scenario, the formation of complex molecules as result of hydrogenation or oxygenation of volatile species are expected to be severely affected.

Molecular clouds (MCs) are exposed to Galactic and extragalactic cosmic rays (CR) that trigger several physical and physicochemical changes, including gas and grain heating and molecular destruction and formation. Here we present a theoretical model describing the energy delivered by CRs, composed of protons, alphas, and electrons taken from Voyager I measurements, into a typical MC with 5400 M ☉ (composed mainly of H with a density law of r −1.2) and size around 1 × 106 au. The calculation was performed employing the Monte Carlo toolkit GEANT4 to obtain the energy deposition per mass from several types of secondary particles (considering nuclear and hadron physics). The results indicate that incoming protons contribute to most of the energy delivered in the MC in all regions (maximum ∼230 MeV g−1 s−1 at outer regions of the cloud). Secondary electrons are the second most important component for energy deposition in almost all layers of the MC and can deliver an energy rate of ∼130 MeV g−1 s−1 in the outer region of the MC. Other cascade particles have their major energy delivery in the central and denser core of the MC. From a temperature model (considering CR data from Voyager I), we observed (i) a small bump in temperature at the distance of 3 × 103–2 × 104 au from the center, (ii) a rapid temperature decrease (roughly 7 K) between the outer layer and the second most outer layer, and (iii) that, at a distance of 5 × 104 au (Av > 10), the gas temperature of the MC is below 15 K.

C2H4O2 isomers, methyl formate (HCOOCH3), acetic acid (CH3COOH) and glycoaldehyde (HOCH2CHO), have been detected in a lot of sources in ISM. However, their abundances are very different, with methyl formate much more abundant than the other two isomers. This fact may be related to the different destruction by ionizing radiation of these molecules. The goal of this work is experimentally study the photodissociation processes of methyl formate and acetic acid ices when exposed to broadband soft X-ray from 6 up to 2000 eV. The experiments were performed coupled to the SGM beamline in the Brazilian Synchrotron Light Source (LNLS/CNPEM) at Campinas, Brazil. The simulated astrophysical ices (12K) were monitored throughout the experiment using infrared vibrational spectroscopy. The analysis of processed ices allowed the determination of the effective destruction cross sections of the parent molecules as well as the effective formation cross section of daughter molecular species. The relative abundance between acetic acid and methyl formate (NCH3COOH/NHCOOCH3) in different astronomical scenarios and their column density evolution in the presence of X-rays were calculated and our results suggests that such radiation field can be one of the factors that explain the difference in the isomers C2H4O2 abundances. We also quantified the daugther species after the establishment of a chemical equilibrium in the samples.

The employment of soft X-rays and swift ions has been used in laboratory to simulate the physicochemical processing of astrophysical ice analogs by energetic photons and cosmic rays. This processing includes excitation, ionization and molecular dissociation, desorption, as well as triggers the formation of new compounds. Here we present some results from experiments employing infrared spectroscopy in two different laboratories: LNLS/CNPEM in Campinas/Brazil and GANIL/CIRIL/CIMAP in Caen/France. Among the results are the formation of alkenes and aromatic compounds during the irradiation of saturated hydrocarbon-containing ices by cosmic ray analogs, the production of the nucleobase adenine during soft X-ray photolysis of N2:CH4 ice, as well as the formation of peptide bonds during the bombardment of frozen glycine by cosmic ray analogs. The interaction between cosmic ray analogs and ionizing soft X-rays probed in the laboratory allows us to identify reaction routes that lead to chemistry enhancement of astrophysical ices and help us put constrains in prebiotic chemistry.

In this work, one intends to computationally simulate and investigate, via thermochemical calculations, how the chemical environment influences some molecular properties, such as IR spectra and absorption cross section, of individual species embedded in the solid phase employing the Polarized Continuum Model (PCM) approach. The trial molecules used here to check these effects are CO, CO2 and H2O. The solid phase (bulk ice) is simulated using different dielectric constant values representing different types of astrophysical ice at PCM approach. The effect of temperature is also investigated since it is known it affects the dielectric constant of the solvent medium.

In this combined experimental-theoretical work we focus on the physical and chemical changes induced by soft X-rays on sulfur dioxide (SO2) ice at a very low temperature, in an attempt to clarify and quantify its survival and chemical changes in some astrophysical environments. SO2 is an important constituent of some Jupiter moons and has also been observed in ices around protostars. The measurements were performed at the Brazilian Synchrotron Light Source (LNLS/CNPEM), in Campinas, Brazil. The SO2 ice sample (12 K) was exposed to a broadband beam of mainly soft X-rays (6-2000 eV) and in situ analyses were performed by IR spectroscopy. The X-ray photodesorption yield (upper limit) was around 0.25 molecules per photon. The values determined for the effective destruction (SO2) and formation (SO3) cross sections were 2.5 × 10-18 cm2 and 2.1 × 10-18 cm2, respectively. The chemical equilibrium (88% of SO2 and 12% of SO3) was reached after the fluence of 1.6 × 1018 photons cm-2. The SO3 formation channels were studied at the second-order Moller-Plesset perturbation theory (MP2) level, which showed the three most favorable reaction routes (ΔH < -79 kcal mol-1) in simulated SO2 ice: (i) SO + O2 → SO3, (ii) SO2 + O → SO3, and (iii) SO2 + O+ → SO3+ + e- → SO3. The amorphous solid environment effect decreases the reactivity of intermediate species towards SO3 formation, and ionic species are even more affected. The experimentally determined effective cross sections and theoretical reaction channels identified in this work allow us to better understand the chemical evolution of certain sulfur-rich astrophysical environments.

In order to investigate the role of medium mass cosmic rays and energetic solar particles in the processing of N2-rich ice on frozen moons and cold objects in the outer solar system, the bombardment of an N2 : H2O : NH3 : CO2 (98.2 : 1.5 : 0.2 : 0.1) ice mixture at 16 K employing 15.7 MeV 16O5+ was performed. The changes in the ice chemistry were monitored and quantified by Fourier transformed infrared spectroscopy (FTIR). The results indicate the formation of azide radicals (N3), and nitrogen oxides, such as NO, NO2, and N2O, as well as the production of CO, HNCO, and OCN−. The effective formation and destruction cross-sections are roughly on the order of 10−12 cm2 and 10−13 cm2, respectively. From laboratory molecular analyses, we estimated the destruction yields for the parent species and the formation yields for the daughter species. For N2, this value was 9.8 × 105 molecules per impact of ions, and for the most abundant new species (N3), it was 1.1 × 105 molecules per impact of ions. From these yields, an estimation of how many species are destroyed or formed in a given timescale (108 years) in icy bodies in the outer solar system was calculated. This work reinforces the idea that such physicochemical processes triggered by cosmic rays, solar wind, and magnetospheric particles (medium-mass ions) in nitrogen-rich ices may play an important role in the formation of molecules (including pre-biotic species precursors such as amino acids and other “CHON” molecules) in very cold astrophysical environments, such as those in the outer region of the solar system (e.g. Titan, Triton, Pluto, and other KBOs).

International audience; This work presents a physicochemical study of frozen amorphous methane (at 16 K) under bombardment by medium-mass ions (15.7 MeV 16O5+) with implications for icy bodies in the outer Solar System exposed to the action of cosmic rays and energetic particles. The experiment was performed at the Grand Accélérateur National d'Ions Lourds (GANIL) located in Caen, France. The results demonstrate that irradiation of CH4-containing ices by swift medium mass ions with delivered energy covering both stopping power regimes until its implantation on ice (i.e. electronic and nuclear) leads to the production of many hydrocarbons, such as C2H2, C2H4, C2H6, and C3H8 (the most abundant daughter species produced). Values for the effective dissociation cross section of CH4 and the average value for the effective formation cross-sections of its daughter species were about 10−14 cm2 and 10−15 cm2, respectively. The half-life of methane ice in the presence of swift medium mass ions extrapolated to some outer Solar System environments is estimated to be around 106 years. The measured sputtering yield of methane due to incoming swift ions was about 7.30 × 105 molecules per impact. Such parameters can be used as models to estimate the amount of CH4 and other molecular species desorbed from the icy surfaces that are constantly being incorporated to the gaseous atmosphere in the vicinity of these outer Solar System bodies due to the presence of energetic particles and cosmic rays.

Charge state spectra of krypton ions generated after ionization (by a single photon) of the L shell have been measured by using the PEPICO technique. Relative abundances of Kr q+ ions in charge state up to 8+ were obtained using monochromatized synchrotron radiation. A comparison with other experimental and theoretical data is presented.

Branching ratios of krypton ions were measured around the 2s edge using synchrotron radiation. The present results are compared with existing theoretical and experimental values. Collective effects of electrons in the 2s orbital might have a significant action. It is shown that one-electron photoionization is enhanced just below this inner-shell threshold. This is due to the fact that the transition of an inner shell electron changes the self-consistent field acting upon the outer electrons, allowing one or several of them to be ejected. This effect is very pronounced in krypton around the 2s edge, where a strong maximum in the seven-fold charged-ion yield occurs near the Kr 2s threshold.

In this combined experimental-theoretical work we focus on the physical and chemical changes induced by soft X-rays on sulfur dioxide (SO

RATIONALE An interesting class of volatile compounds, the monoterpenes, is present in some plants although their functions are not yet fully understood. We have studied the interaction of the camphor molecule with monochromatic high-energy photons (synchrotron radiation) using time-of-flight mass spectrometry and coincidence techniques. METHODS A commercial sample of S-camphor was admitted into the vacuum chamber, without purification, through an inlet system. Monochromatic light with energy around the C 1s edge was generated by the TGM beamline at the Brazilian Synchrotron Facility. A Wiley-McLaren mass spectrometer was used to characterize and detect the ions formed by the camphor photoionization. The data analysis was supported by energy calculations. RESULTS Although the fragmentation patterns were basically the same at 270 eV and 330 eV, it was observed that above the C 1s edge the contribution to the spectrum from lower mass/charge fragment ions increased, pointing to a higher degree of dissociation of the molecule. Projections of the PEPIPICO spectra demonstrated the existence of unstable doubly charged species. The Gibbs free energy was calculated using the Moller-Plesset perturbation theory (MP2) for the neutral, singly and doubly excited camphor molecule. CONCLUSIONS Our PEPIPICO spectrum clearly demonstrated the formation of doubly ionic dissociative species. From a slope analysis, we propose a secondary decay after a deferred charge separation mechanism in which, after a few steps, the camphor dication dissociates into C2 H3 (+) and C3 H5 (+) . This is the main relaxation route observed at 270 eV and 330 eV. The large energy difference between the mono and the dication (of the order of 258.2 kcal/mol) may explain the experimentally observed absence of stable dications in the spectra, because their formation is disadvantaged energetically.

We present a code, called NKABS, to determine optical constants (complex refractive index) of thin films directly from the absorbance data in the infrared. The code is written in the Python language, which is more accurate and faster than previous methods in the literature. For solving the Kramers-Kronig relationship, we used the Maclaurin's methodology. Unlike other codes, which found convergence in 30-40 iterations, the NKABS reach the convergence in just 4 or 5 iterations. Additionally, to evaluate the error, this code calculates the MAPE (Mean Absolute Percentage Error) and the chi-square χ(2). The typical MAPE error obtained using NKABS is less than 1×10(-3)%. To illustrate the functionality of this code, we calculate the optical constants in the infrared spectral region of 28 different samples of astrophysical interest at different temperatures (10-300K), which simulates molecules in space environments, mostly the ones called astrophysical ices. The samples were obtained from the condensation of pure gases (e.g. CO, CO2, NH3, SO2), from the sublimation in vacuum of pure liquids (e.g. water, acetone, acetonitrile, acetic acid, formic acid, ethanol and methanol) and from mixtures of different species (e.g. H2O:CO2, H2O:CO:NH3, H2O:CO2:NH3:CH4). Additionally films of solid biomolecules samples of astrochemistry/astrobiology interest (e.g. glycine, adenine) were probed. The code and the data-base obtained here are available on-line. The NKABS can also be employed to calculate refractive index of processed samples (by heating or radiation). Such data and the refractive index of virgin samples are required as input in several astrophysical models that calculate the radiative transfer in dusty astrophysical environments such as protoplanetary disks and circumstellar environments as well as dense molecular clouds.

Acetone, one of the most important molecules in organic chemistry, also a precursor of prebiotic species, was found in the interstellar medium associated with star-forming environments. The mechanisms proposed to explain the gas phase abundance of interstellar acetone are based on grain mantle chemistry. High energy photons coming from the stellar radiation field of the nearby stars interact with the ice mantles on dust grains leading to photoionization, photodissociation, and photodesorption processes. In this work we investigate the photodesorption and the photostability of pure acetone ices due to soft X-ray impact. Absolute desorption yields per photon impact for the main positive ionic fragments were determined at the O 1s resonance energy (531.4 eV). The photostability of acetone ice was studied by exposure to different irradiation doses with a white beam of synchrotron radiation. The degradation of the ice was monitored by NEXAFS around the O 1s threshold. From this study we determine the photodiss...

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The electronic excitation and associated ionic dissociation of the carvone molecule have been studied around the oxygen 1s edge, using synchrotron radiation and time-of-flight techniques. Photoabsorption spectrum (total ion yield) and mass spectra have been obtained in the range between 520 and 545 eV. For the sake of comparison, carvone mass spectra have also been obtained following valence (21.21 eV) and core (carbon 1s) ionization. Fragmentation of the molecule is seen to be greatly enhanced following core excitation. Around the oxygen 1s edge, we observe an extensive fragmentation of the molecular skeleton, as exemplified by the appearance of several previously unreported ions: H + , H 2 + , CH + , CH 2 + and CH 3 + , which are not formed at low energies. A maximum is observed at 536 eV photon energy in the relative intensity of the oxygen-containing ions O + , O 2+ and OH + , as an evidence for the existence of site-selective fragmentation of the carvone molecule excited around the O 1s edge. Absolute values for the photoionization and photodissociation cross sections were estimated using the molecular additive rule.

In dense and cold regions of the interstellar medium (ISM), molecules may be adsorbed onto dust grains to form the ice mantles. Once formed, they can be processed by ionizing radiation coming from stellar or interstellar medium leading to formation of several new molecules in the ice. Among the different kind of ionizing radiation, cosmic rays play an important role in the solid-phase chemistry because of the large amount of energy deposited in the ices. The physicochemical changes induced by the energetic processing of astrophysical ices are recorded in a intrinsic parameter of the matter called complex refractive index (CRI). In this paper, we present for the first time a catalogue containing 39 complex refractive indices (n, k) in the infrared from 2.0 - 16.6 micrometer for 13 different water-containing ices processed in laboratory by cosmic ray analogs. The calculation was done by using the NKABS (acronym of determination of N and K from ABSorbance data) code, which employs the Lambert-Beer and Kramers-Kronig equations to calculate the values of n and k. The results are also available at the website: http://www1.univap.br/gaa/nkabs-database/data.htm. As test case, a H2O:NH3:CO2:CH4 ice was employed in a radiative transfer simulation of a prototoplanetary disk to show that these data are indispensable to reproduce the spectrum of YSOs containing ices.

This work analyzes the physico-chemical effects due to electron irradiation, as e.g. caused by the solar wind, on pure methanol (CH 3- OH) ice. Methanol has been detected in gas and condensed phases in several astrophysical environments, such as comets, asteroids,toward star forming regions and molecular clouds. In some of these environments, methanol is the most abundant specie after waterice. The interaction of ionizing agents with methanol ice induces the production of ionized species, leading to the formation of new com-pounds. In this work, pure methanol ice (at 142 K) was irradiated, in ultra-high vacuum regime, with 800 eV electrons, thus simulatingthe wind in frozen surfaces. The desorbed ions were analyzed using time-of-flight mass spectrometry. The results show the formation ofprotonated species, such as (CH 3 OH)H + ,H 2 COH + ,C 2 H þ3 and HCO . Absolute desorption yields were determined and compared withresults available in the literature from similar experiments. The ionic desorption rate is an important parameter in surface chemistry. It isoften approximated in chemical evolution models of astrophysical environments, due to the lack of experimental data. 2013 COSPAR. Published by Elsevier Ltd. All rights reserved.

Photoionization and photofragmentation studies of formic acid (HCOOH) are performed for the valence shell electron ionization process. The total and partial ion yield of gaseous HCOOH were collected as a function of photon energy in the ultraviolet region, between 11.12 and 19.57 eV. Measurements of the total and partial ion yield of gaseous formic acid molecule are performed with a time-of-flight mass spectrometer at the Synchrotron Light Brazilian Laboratory. Density functional theory and time dependent density functional theory are employed to calculate the ground and excited electronic state energies of neutral and ionic formic acid as well as their fragments and normal vibration modes. The ionization potential energies, the stability of electronic excited states of HCOOH(+), and the energies of opening fragmentation channels are estimated from theoretical-experimental analysis. Additionally, the main formic acid photofragmentation pathways by exposition of photons within that energy range are determined experimentally. These produced ions primarily have the following mass/charge ratios: 46 (HCOOH(+)), 45 (COOH(+)), 29 (HCO(+)), and 18 (H(2)O(+)).

The formation of C=C and C≡C bonds from the processing of pure c-C6H12 (cyclo- hexane) and mixed H2O:NH3:c-C6H12 (1:0.3:0.7) ices by highly-charged, and energetic ions (219 MeV 16 O 7+ and 632 MeV 58 Ni 24+ ) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ices analogs. The measurements were performed inside a high vacuum chamber at the heavy-ion acceler- ator GANIL (Grand Accelerateur National d'Ions Lourds) i n Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared (FTIR) spectrometry at different ion fluences. Dis- sociation cross section of cyclohexane and its half-life in astrophysical environments were determined. A comparison between spectra of bombarded ices and young stellar sources in- dicates that the initial composition of grains in theses env ironments should contain a mixture of H2O, NH3, CO (or CO2), simple alkanes, and CH3OH. Several species containing double or triple bounds were identified in the radiochemical produc ts, such as hexene, cyclohexene, benzene, OCN − , CO, CO2, as well as several aliphatic and aromatic alkenes and alkynes. The results suggest an alternative scenario for the product ion of unsaturated hydrocarbons and possibly aromatic rings (via dehydrogenation processes) in interstellar ices induced by cosmic ray bombardment.

14 pags., 10 figs., 2 tabs., app., We use experimental mid-infrared optical constants and extended effective medium approximations to determine the porosity and the band strengths of multi-phase composite ices grown at 30 K. A set of porous H2O:CH4 ices are taken as a prototypical example. As a benchmark and proof of concept, the stoichiometry of the ice constituents is retreived with good accuracy from the refractive indices and the extinction coefficients of the reference binary ice mixtures with known compositions. Accurate band strengths are then calculated from experimental mid-infrared spectra of complex ices. We notice that the presence of pores has only a small effect on the overall band strengths, whereas a water dilution can considerably alter them. Different levels of porosity are observed depending on the abundance of methane used as a gas contaminant premixed with water prior to background deposition. The absorption profiles are also found to vary with deposition rate. To explain this, we use Monte Carlo simulations and we observe that the deposition rate strongly affects the pore size distribution as well as the ice morphology through reorganization processes. Extrapolated to genuine interstellar ices, the methodology presented in this paper can be used to evaluate the porosity and to quantify the relative abundances from observational data., Part of this work was supported by NOVA, the , aNetherlands Research School for Astronomy and Vici grant from the Netherlands Organisation for Scientic Research (NWO). J.-B.B. is grateful for support from the Marie Sklodowska Curie actions and the Intra-European Fellowship (FP7- PEOPLE-2011-IEF-299258). S.C. is supported by the Netherlands Organization for Scientific Research (NWO). B.M. and J. O. were supported by the MINECO of Spain under grant FIS2013-48087-C2-1P. S.P. thanks the Brazilian agencies CNPq, CAPES, INCT-A, and FAPESP (JP2009/18304-0; DR2013/07657-5) for financial support.

Despite the extensive search for glycine (NH₂CH₂COOH) and other amino acids in molecular clouds associated with star-forming regions, only upper limits have been derived from radio observations. Nevertheless, two of glycine's precursors, formic acid and acetic acid, have been abundantly detected. Although both precursors may lead to glycine formation, the efficiency of reaction depends on their abundance and survival in the presence of a radiation field. These facts could promote some favoritism in the reaction pathways in the gas phase and solid phase (ice). Glycine and these two simplest carboxylic acids are found in many meteorites. Recently, glycine was also observed in cometary samples returned by the Stardust space probe. The goal of this work was to perform theoretical calculations for several interstellar reactions involving the simplest carboxylic acids as well as the carboxyl radical (COOH) in both gas and solid (ice) phase to understand which reactions could be the most favorable to produce glycine in interstellar regions fully illuminated by soft X-rays and UV, such as star-forming regions. The calculations were performed at four different levels for the gas phase (B3LYP/6-31G*, B3LYP/6-31++G**, MP2/6-31G*, and MP2/6-31++G**) and at MP2/6-31++G** level for the solid phase (ice). The current two-body reactions (thermochemical calculation) were combined with previous experimental data on the photodissociation of carboxylic acids to promote possible favoritism for glycine formation in the scenario involving formic and acetic acid in both gas and solid phase. Given that formic acid is destroyed more in the gas phase by soft X-rays than acetic acid is, we suggest that in the gas phase the most favorable reactions are acetic acid with NH or NH₂OH. Another possible reaction involves NH₂CH₂ and COOH, one of the most-produced radicals from the photodissociation of acetic acid. In the solid phase, we suggest that the reactions of formic acid with NH₂CH or NH₂CH₂OH are the most favorable from the thermochemical point of view.

The methyl formate molecule (HCOOCH3) is one of the most abundant molecules observed in hot molecular cores. Together with acetic acid and the sugar glycolaldehyde, these C2H4O2 molecules are the first triad of isomers detected in interstellar clouds. However, the observations point to a high enhancement in the abundance of methyl formate, which can reach up to 100 times the amount of its second abundant isomer, acetic acid. The observational abundance difference between these isomers has been subject of several works, invoking different formation pathways or survival rates. In this work we present an experimental and theoretical study of photoionization and photodissociation processes of HCOOCH3, to point out clues about its survival to high-energy photons observed in some interstellar environments. In order to obtain the most stable C2H4O2 cations and dications dissociation pathways, spectroscopic and computational methods were used. The measurements were taken employing soft X-ray photons with energies around carbon 1s and oxygen 1s resonances, while the calculations were performed at B3LYP/cc-pVDZ level, at the experimental pressure and temperature. Mass spectra of the photoproduced fragments were obtained using photoelectron photoion coincidence method. The main photodissociation channels are in agreement with the most favourable calculated pathways. Photoionization and photodissociation cross-sections were also determined. The results suggest that the observed high abundance of methyl formate could not be attributed to photodissociation processes.

An experimental photochemistry study involving gas- and solid-phase amino acids (glycine, DL-valine, DL-proline) and nucleobases (adenine and uracil) under soft X-rays was performed. The aim was to test the molecular stabilities of essential biomolecules against ionizing photon fields inside dense molecular clouds and protostellar discs analogs. In these environments, the main energy sources are the cosmic rays and soft X-rays. The measurements were taken at the Brazilian Synchrotron Light Laboratory (LNLS), employing 150-eV photons. In situ sample analysis was performed by time-of-flight mass spectrometer (TOF-MS) and Fourier transform infrared (FTIR) spectrometer, for gas- and solid-phase analysis, respectively. The half-life of solid-phase amino acids, assumed to be present at grain mantles, is at least 3 × 10 5 and 3 × 10 8 yr inside dense molecular clouds and protoplanetary discs, respectively. We estimate that for gas-phase compounds these values increase 1 order of magnitude since the dissociation cross-section of glycine is lower in gas phase than in solid phase for the same photon energy. The half-life of solid-phase nucleobases is about 2–3 orders of magnitude longer than found for amino acids. The results indicate that nucleobases are much more resistant to ionizing radiation than amino acids. We consider these implications for the survival and transfer of biomolecules in space environments.