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In this work, we focus on the study of radiation-induced desorption processes that occurred in acetonitrile ice irradiated by broad-band X-rays (6 eV to 2 keV) monitored by Fourier transform infrared spectroscopy at different radiation fluences. In a previous work, we used the procoda code to derive the chemical evolution of the ice. Here, we have observed that the acetonitrile desorbed column density is at least two orders of magnitude larger than the desorbed column densities of daughter or granddaughter molecular species at chemical equilibrium stage. This indicates that total desorption column density is mainly governed by the father molecule, as also previously hypothesized in experimental studies. This occurs basically because the acetonitrile column density is larger than the other ones. In particular, at chemical equilibrium acetonitrile desorption column density represents almost 98 per cent of the total, while it is close to 1  per cent for H, CN, and CH2, the species with larger molecular desorption percentages at chemical equilibrium. Another derived quantity is what we called intrinsic desorption rate, which is a number per second for individual species. Some of the larger intrinsic desorption rates were 6.2 × 10−6 (CH3CN), 6.2 × 10−6 (CN), 5.7 × 10−6 (H), 5.7 × 10−6 (CH2), and 4.4 × 10−6 (C2N2). These results help to put constraints in astrochemical models and can also be useful to clarify some astronomical radio observations. [ABSTRACT FROM AUTHOR]

Glycolaldehyde (HOCH2CHO) is the most straightforward sugar detected in the Interstellar Medium (ISM) and participates in the formation pathways of molecules fundamental to life, red such as ribose and derivatives. Although detected in several regions of the ISM, its formation route is still debated and its abundance cannot be explained only by reactions in the gas phase. This work explores a new gas-phase formation mechanism for glycolaldehyde and compares the energy barrier reduction when the same route happens on the surface of amorphous ices. The first step of the mechanism involves the formation of a carbon–carbon bond between formaldehyde (H2CO) and the formyl radical (HCO), with an energy barrier of 27 kJ mol−1 (gas-phase). The second step consists of barrierless hydrogen addition. Density functional calculations under periodic boundary conditions were applied to study this reaction path on 10 different amorphous ice surfaces through an Eley–Rideal type mechanism. It was found that the energy barrier is reduced on average by 49 per cent, leading in some cases to a 100 per cent reduction. The calculated adsorption energy of glycolaldehyde suggests that it can be promptly desorbed to the gas phase after its formation. This work, thus contributes to explaining the detected relative abundances of glycolaldehyde and opens a new methodological framework for studying the formation routes for Complex Organic Molecules (COMs) in interstellar icy grains. [ABSTRACT FROM AUTHOR]

In this study, we employed broad-band X-rays (6–2000 eV) to irradiate the frozen acetone CH3COCH3, at the temperature of 12 K, with different photon fluences up to 2.7 × 1018 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 × 1018 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. Time-scales for ices, at hypothetical snow line distances, to reach chemical equilibrium around several compact and main-sequence X-ray sources are given. We estimate time-scales of 18 d, 3.6 and 1.8 months, 1.4 × 109–6 × 1011 yr, 600 and 1.2 × 107 yr, and 107 yr, 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. [ABSTRACT FROM AUTHOR]

Nitrous oxide, N2O, is found in the interstellar medium associated with dense molecular clouds and its abundance is explained by active chemistry occurring on N2 rich ice surfaces of dust grains. Such regions are being constantly exposed to ionizing radiation that triggers chemical processes which change molecular abundances with time. Due to its non-zero dipole moment, N2O can be used as an important tracer for the abundance of N2 in such regions as well as for characterization of nitrogen content of ices in outer bodies of Solar system. In this work, we experimentally investigate the resistance of frozen N2O molecules against radiation in attempt to estimate their half-life in astrophysical environments. All the radiolysis products, such as NO2 and NO, were identified by Fourier transform infrared spectroscopy. The infrared absorbance as a function of fluence is modified by ice compaction and by radiolysis, the compaction being dominant at the beginning of the ice processing. The N2O destruction cross-section as well the formation cross-sections of the products NxOy (x = 1-2 and y = 1-5) oxides and ozone (O3) by 1.5 MeV 14N+ ion beam are determined. The characterization of radiation resistance of N2O in cold astrophysical environments is relevant since it yields limits for the nitrogen abundance where the N2O molecule is used to indirectly derive its concentration. The half-life of solid N2O molecules dissociated by medium-mass cosmic rays at Pluto's orbit and at the interstellar medium is estimated. [ABSTRACT FROM AUTHOR]

In the dense and cold regions of the interstellar medium, molecules can be adsorbed on to dust grains to form ice mantles. Once formed, these can be processed by ionizing radiation coming from the stellar or interstellar medium, leading to the formation of several new molecules in the ice. Among the different types of ionizing radiation, cosmic rays play an important role in 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 the complex refractive index. In this paper, for the first time, we present a catalogue containing 39 complex refractive indices (n, k) in the infrared from 5000 to 600 cm-1 (2.0-16.6 µm) for 13 different water-containing ices processed in the laboratory by cosmic ray analogues. The calculation was performed using the NKABS--an acronym of the 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 following web site: http://www1.univap.br/gaa/nkabs-database/data.htm. As a test case, H2O:NH3:CO2:CH4 ice was employed in a radiative transfer simulation of a protoplanetary disc to show that these data are indispensable to reproduce the spectrum of ices containing young stellar objects. [ABSTRACT FROM AUTHOR]

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 and 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. [ABSTRACT FROM AUTHOR]

We present experimental results obtained from photoionization and photodissociation processes of abundant interstellar CH3-X type organic molecules like methanol (CH3OH), methylamine (CH3NH2) and acetonitrile (CH3CN) as alternative route for the production of in interstellar and star-forming environments. The measurements were taken at the Brazilian Synchrotron Light Laboratory (LNLS), employing soft X-ray photons with energies between 200 and 310 eV and time-of-flight (TOF) mass spectrometry. Mass spectra were obtained using the photoelectron–photoion coincidence techniques. Absolute averaged cross-sections for production by soft X-rays were determined. We have found that, among the channels leading to molecular dissociation, the yield could reach values up to 0.7 per cent for single photoionization process and up to 4 per cent for process involving double photoionization. The photoproduction cross-section due to the dissociation of the studied organic molecules by photons over the C1s edge (200–310 eV) were about 0.2–1.4 × 10−18 cm2. Adopting the typical X-ray luminosity which best fit the observational data for AFGL 2591 we derive an estimative for the photoproduction rate due to methyl compound dissociation process. The highest value for the column density from methanol dissociation by soft X-rays, assuming a steady state scenario, was about 1011 cm2, which gives the fraction of the photoproduced of about 0.05 per cent, as in the case of dense molecular cloud AFGL 2591. Despite the extreme small value, this represent a new and alternative source of into dense molecular clouds and it is not been considered as yet in interstellar chemistry models. [ABSTRACT FROM AUTHOR]