We investigated the behavior of H 2 , main constituent of the gas phase in dense clouds, after collision with amorphous solid water (ASW) surfaces, one of the most abundant chemical species of interstellar ices. We developed a general framework to study the adsorption dynamics of light species on interstellar ices. We provide binding energies and their distribution, sticking probabilities for incident energies between 1 meV and 60 meV, and thermal sticking coefficients between 10 and 300 K for surface temperatures from 10 to 110 K. We found that the sticking probability depends strongly on the adsorbate kinetic energy and the surface temperature, but hardly on the angle of incidence. We observed finite sticking probabilities above the thermal desorption temperature. Adsorption and thermal desorption should be considered as separate events with separate time scales. Laboratory results for these species have shown a gap in the trends attributed to the differently employed experimental techniques. Our results complement observations and extend them, increasing the range of gas temperatures under consideration. We plan to employ our method to study a variety of adsorbates, including radical and charged species.

Water is one of the most abundant molecules in the form of solid ice phase in the different regions of the interstellar medium (ISM). This large abundance cannot be properly explained by using only traditional low temperature gas-phase reactions. Thus, surface chemical reactions are believed to be major synthetic channels for the formation of interstellar water ice. Among the different proposals, hydrogenation of atomic O (i.e., 2H + O → H2O) is a chemically “simple” and plausible reaction toward water formation occurring on the surfaces of interstellar grains. Here, novel theoretical results concerning the formation of water adopting this mechanism on the crystalline (010) Mg2SiO4 surface (a unequivocally identified interstellar silicate) are presented. The investigated reaction aims to simulate the formation of the first water ice layer covering the silicate core of dust grains. Adsorption of the atomic O as a first step of the reaction has been computed, results indicating that a peroxo (O22−) group is formed. The following steps involve the adsorption, diffusion and reaction of two successive H atoms with the adsorbed O atom. Results indicate that H diffusion on the surface has barriers of 4−6 kcal mol−1, while actual formation of OH and H2O present energy barriers of 22−23 kcal mol−1. Kinetic study results show that tunneling is crucial for the occurrence of the reactions and that formation of OH and H2O are the bottlenecks of the overall process. Several astrophysical implications derived from the theoretical results are provided as concluding remarks.

A theoretical study of the structure and mid infrared (IR) spectra of interstellar hydrocarbon dust analogs is presented, based on DFT calculations of amorphous solids. The basic molecular structures for these solids are taken from two competing literature models. The first model considers small aromatic units linked by aliphatic chains. The second one assumes a polyaromatic core with hydrogen and methyl substituents at the edges. The calculated spectra are in reasonably good agreement with those of aliphatic-rich and graphitic-rich samples of hydrogenated amorphous carbon (HAC) generated in our laboratory. The theoretical analysis allows the assignment of the main vibrations in the HAC spectra and shows that there is a large degree of mode mixing. The calculated spectra show a marked dependence on the density of the model solids, which evinces the strong influence of the environment on the strengths of the vibrational modes. The present results indicate that the current procedure of estimating the hydrogen and graphitic content of HAC samples through the decomposition of IR features into vibrational modes of individual functional groups is problematic owing to the mentioned mode mixing and to the difficulty of assigning reliable and unique band strengths to the various molecular vibrations. Current band strengths from the literature might overestimate polyaromatic structures. Comparison with astronomical observations suggests that the average structure of carbonaceous dust in the diffuse interstellar medium lies probably in between those of the two models considered, though closer to the more aliphatic structure.

Contact. The increasing capabilities of space missions like the James Webb Space Telescope or ground-based observatories like the European Extremely Large Telescope demand high quality laboratory data of species in astrophysical conditions for the interpretation of their findings. Aims. We provide new physical and spectroscopic data of solid methanol that will help to identify this species in astronomical environments. Methods. Ices were grown by vapour deposition in high vacuum chambers. Densities were measured via a cryogenic quartz crystal microbalance and laser interferometry. Absorbance infrared spectra of methanol ices of different thickness were recorded to obtain optical constants using an iterative minimization procedure. Infrared band strengths were determined from infrared spectra and ice densities. Results. Solid methanol densities measured at eight temperatures vary between 0.64 g cm−3 at 20 K and 0.84 g cm−3 at 130 K. The visible refractive index at 633 nm grows from 1.26 to 1.35 in that temperature range. New infrared optical constants and band strengths are given from 650 to 5000 cm−1 (15.4–2.0 μm) at the same eight temperatures. The study was made on ices directly grown at the indicated temperatures, and amorphous and crystalline phases have been recognized. Our optical constants differ from those previously reported in the literature for an ice grown at 10 K and subsequently warmed. The disagreement is due to different ice morphologies. The new infrared band strengths agree with previous literature data when the correct densities are considered.

In this work, we present the results of our investigation into the chemistry of Z- and E-cyanomethanimine (HNCHCN), both of which are possible precursors to the nucleobase adenine. Ab initio quantum chemical calculations for a number of reactions with atomic hydrogen were carried out. We find that the reaction H + Z/E-HNCHCN leading both to H-addition as well as H2-abstraction proceed via similar short-range barriers with bimolecular rate coefficients on the order of ∼10−17 cm3 s−1. These results were then incorporated into astrochemical models and used in simulations of the giant molecular cloud G+0.693. The calculated abundances obtained from these models were compared with previous observational data and found to be in good agreement, with a predicted [Z/E] ratio of ∼3—somewhat smaller than the previously derived value of 6.1 ± 2.4. We find that the [Z/E] ratio in our simulations is due mostly to ion-molecule destruction rates driven by the different permanent dipoles of the two conformers. Based on these results, we propose a general rule-of-thumb for estimating the abundances of isomers in interstellar environments, which we call the “relative dipole principle.”

With the presence of evermore complex S-bearing molecules being detected lately, studies of their chemical formation routes need to keep up the pace to rationalize observations, suggest new candidates for detection, and provide input for chemical evolution models. In this paper, we theoretically characterize the hydrogenation channels of OCS on top of amorphous solid water (ASW) as an interstellar dust grain analog in molecular clouds. Our results show that the significant reaction outcome is trans-HC(O)SH, a recently detected prebiotic molecule toward G+0.693. The reaction is diastereoselective, explaining the apparent absence of the cis isomer in astronomical observations. We found that the reaction proceeds through a highly localized radical intermediate (cis-OCSH), which could be essential in the formation of other sulfur-bearing complex organic molecules due to its slow isomerization dynamics on top of ASW.

Context. The diffusion of volatile species on amorphous solid water ice affects the chemistry on dust grains in the interstellar medium as well as the trapping of gases enriching planetary atmospheres or present in cometary material. Aims. The aim of the work is to provide diffusion coefficients of CH 4 on amorphous solid water (ASW) and to understand how they are affected by the ASW structure. Methods. Ice mixtures of H 2 O and CH 4 were grown in different conditions and the sublimation of CH 4 was monitored via infrared spectroscopy or via the mass loss of a cryogenic quartz crystal microbalance. Diffusion coefficients were obtained from the experimental data assuming the systems obey Fick's law of diffusion. Monte Carlo simulations were used to model the different amorphous solid water ice structures investigated and were used to reproduce and interpret the experimental results. Results. Diffusion coefficients of methane on amorphous solid water have been measured to be between 10 −12 and 10 −13 cm 2 s −1 for temperatures ranging between 42 K and 60 K. We show that diffusion can differ by one order of magnitude depending on the morphology of amorphous solid water. The porosity within water ice and the network created by pore coalescence enhance the diffusion of species within the pores. The diffusion rates derived experimentally cannot be used in our Monte Carlo simulations to reproduce the measurements. Conclusions. We conclude that Fick's law can be used to describe diffusion at the macroscopic scale, while Monte Carlo simulations describe the microscopic scale where trapping of species in the ices (and their movement) is considered.

The recent wave of detections of interstellar aromatic molecules has sparked interest in the chemical behavior of aromatic molecules under astrophysical conditions. In most cases, these detections have been made through chemically related molecules, called proxies, that implicitly indicate the presence of a parent molecule. In this study, we present the results of the theoretical evaluation of the hydrogenation reactions of different aromatic molecules (benzene, pyridine, pyrrole, furan, thiophene, silabenzene, and phosphorine). The viability of these reactions allows us to evaluate the resilience of these molecules to the most important reducing agent in the interstellar medium, the hydrogen atom (H). All significant reactions are exothermic and most of them present activation barriers, which are, in several cases, overcome by quantum tunneling. Instanton reaction rate constants are provided between 50 K and 500 K. For the most efficiently formed radicals, a second hydrogenation step has been studied. We propose that hydrogenated derivatives of furan, pyrrole, and specially 2,3-dihydropyrrole, 2,5-dihydropyrrole, 2,3-dihydrofuran, and 2,5-dihydrofuran are promising candidates for future interstellar detections.