Context. Most of the molecules identified in the interstellar medium (ISM) are organic compounds and more than 50 have one isomer or more. Statistically, the most stable isomer of a given chemical formula is the most abundant. This occurrence is verified up to similar to 90% of the detected species leading to the so-called minimum energy principle (MEP). Aims. Our main objective is to increase the list of the 14 bis-nitrogen species already detected. We focus on ten CxHyNz isomer families with x = (1, 2, 3), y = (0, 2, 4, 6, 8), z = 2. To this end, we look for a reliable and economic way to provide energy scales. Methods. We employed standard quantum chemistry methods to determine the relative position of each isomer on the energy scales of each family. We systematically applied density functional theory (DFT) treatments using basis sets of increasing size and quality (6-311++G** and cc-pVQZ). When reasonably feasible, we then performed high-level coupled cluster calculations (CCSD) using the same basis sets to refine relative energies. Results. All 14 bis-nitrogen species already identified in the ISM indeed satisfy the MEP. We determine the relative thermodynamic stability of the isomers with a CxHyN2 formula of each of the ten sets (94 compounds altogether), and hightlight those that are potentially detectable. By increasing the number of carbon atoms, we find 15 compounds that are by far the most stable candidates. Conclusions. We confirm that, within the limits of thermodynamics, MEP is an efficient and easily applicable tool for identifying the isomers in a given series that have a greater probability of being detected. Computationally, the combination "B3LYP/cc-pVQZ" provides a suitable compromise for determining energy differences and dipole moments. Clearly, the isomers containing the [NCN] sequence should be prioritized over those with [CNN] in future observation campaigns.

A consensus has progressively developed that the path towards complex organic molecules could be favoured by the icy mantles of interstellar dust particles. However, the question of whether activation energy is required to promote those reactions is open. This work deals with the simplest process thought to increase complexity i.e. successive additions of a single atom (H). Two situations can be considered, the direct additions of H in the gas phase and the atomic hydrogenation processes on water ice surfaces available in the interstellar medium (ISM). The synthesis of methanol, largely discussed in the literature is revisited as a case study. Computational investigations of the reactions leading from CO to CH3OH show that, with [H...(H2O)(n)] complexes as hydrogenation vectors, all steps of the process are barrier-less, contrary to the gas phase process and this, whatever the level of theory considered. The key parameter is the position of the CO + [H...(H2O)(n)] initial system on the global energy scale. At the present level of theory, when H is pre-adsorbed on the ice, the system happens to be high enough above the reaction path, namely, above any intermediates and possible transition states. This is true whatever the dimension of the ice support, even for the simplest model of one H2O molecule. Application of such a simplified synthetic approach, here validated for the synthesis of methanol, could be generalized, providing a simple way to get a fair insight into the important class of atomic hydrogenations on ices in the ISM.

The analysis of the organic matter of meteorites made it possible to identify over 70 amino acids (AA), including 8 of those found in living organisms. However, their relative abundances vary drastically with the type of the carbonaceous chondrite, even for isomers of same chemical formula. In this report, we address the question whether this difference may have its origin in the relative stability of these isomers according to the conditions they experienced when they were formed and after. To this end, we rely on the fact that for most of the species observed so far in the interstellar medium (ISM), the most abundant isomer of a given generic chemical formula is the most stable one (minimum energy principle, MEP). Using quantum density functional theory (DFT) simulations, we investigate the relative stability of the lowest energy isomers of alanine (Ala) and amino butyric acid (ABA) in the neutral, protonated, and zwitterionic structures together with corresponding nitrile precursors. It is shown that β-alanine and γ-ABA are the most stable in a protonated form, whereas α-AA are the most stable in the zwitterionic and nitrile structures. The different composition of the carbonaceous chondrites CIs and CMs could be linked to the chemical context of the aqueous alterations of the parent bodies.

Context. In spite of the permanent damage suffered from the radiation field (cosmic rays, X-rays, and intense UV-visible radiations), interstellar grains are still covered by ices mantles whose role in interstellar chemistry is well beyond any doubt. This clearly means that the destruction of the ice cover has to be counterbalanced by efficient reconstruction mechanisms. Aims. Our goal is to determine whether the ice, which is still present after irradiation, has a catalytic role in the OH + H2 → H2O + H reaction for its own reconstruction. We focus on the three plausible reaction paths depending on the way reactants OH or H2 are adsorbed at the ice surface. Methods. Calculations were performed in both cluster and solid state approaches, using ab-initio post Hartree-Fock methods for small systems, standard density functional theory (DFT) for larger clusters, and periodic solid state DFT with specific formalisms accounting for weak interactions in systems of infinite dimensions. Results. Although the end product is the same, that is namely the reconstruction of one H2O on the subjacent ice, three different reaction paths are found depending on whether H2 reacts with adsorbed OH(ads), wether OH reacts with adsorbed H2(ads) or wether both OH(ads) and H2(ads) are adsorbed on the ice before reacting. In the first case, there is an activation barrier of ~6 kcal mol−1, requiring the tunneling effect for the reaction to proceed, which is in agreement with preceding studies. In the second case, the reaction is a barrierless process leading to the direct reconstruction of the ice. In the third case, the double adsorption increases the activation barrier due to the lowering of the starting energy. This is found regardless of the dimension of the supporting ice aggregates. Conclusions. Icy grain surfaces play a critical role for their own reconstruction in cold, dense interstellar clouds. The prevalence of tunneling over the direct mechanism should strongly depend on the temperature and local environment.

Context. Although H2O is the most important molecular material found in the solid state in the interstellar medium, the chemical routes leading to ice through surface reactions are still a matter of discussion. Three reaction pathways proposed in the past are at the heart of current research: hydrogenation of atomic oxygen, molecular oxygen, and ozone. The reaction network finally leads to a small number of processes giving H2O: H + OH, H2 + OH, and H + H2O2. To these processes, OH + OH should be added. It is known to be efficient in atmospheric chemistry and takes the irradiations of the interstellar grains into account that, directly or indirectly, create a number of OH radicals on and in the icy mantles. Aims. We study the role of the existing ice in its own reconstruction after it is destroyed by the constant irradiation of interstellar grains and focus on the OH + OH reaction in the triplet state. Methods. We used numerical simulations with a high level of coupled cluster ab initio calculations for small water aggregates and methods relevant to density functional theory for extended systems, including a periodic description in the case of solid water of infinite dimensions. Results. OH + OH → H2O + O reaction profiles are reported that take the involvement of an increasing number of H2O support molecules into account. It is found that the top of the barrier opposing the reaction gradually decreases with the number of supporting H2O and falls below the level of the reactants for H2O layers or solid water. Conclusions. In contrast to the gas phase, the reaction is barrierless on water ice. By adding a reconstructed H2O molecule and a free oxygen atom at the surface of the remaining ice, this reaction leaves open the possibility of the ice reconstruction.

Context. Most of the compounds detected in the interstellar medium (ISM) that possess isomers correspond to the thermodynamically most stable isomer of a given chemical formula. Using the minimun energy principle (MEP) as a pragmatic tool is particularly efficient for less than six atoms, but for larger systems combinatorial analysis gives an intractable numbers of isomers.Aims. To make the MEP more applicable, we look for a chemical sieve to filter the thermodynamic data needed to determine which isomers of complex organic molecules (COMs) have higher chances of being present in the ISM. To do so, we investigate whether the nature of the [C,N,O] elementary fragment can be determinant for the stabilization of COMs, taking C2H3NO as a case study.Methods. We employed standard quantum chemistry methods to determine the ordering of fragments and derivatives on the energy scale. Density functional theory treatments were systematically performed, together with high-level coupled cluster calculations to refine relative energies.Results. For C2H3NO we find methylisocyanate CH3NCO, which is a compound that was very recently detected in the ISM, to be the most stable isomer in a corpus of 40 isomers of lowest energy. In neutral form we find the stability ordering of NCO > ONC; the same is true for the negative ion. Attachments of R=H, CH3, C2H5, HC2, H2CCH, and C6H5 and metals Al and Mg to the nitrogen atom of the NCO fragment provide the most stable isomers. The energy differences between the successive isomers on the energy scale R-NCO, R-OCN, R-CNO, and R-ONC are of the same order of magnitude for all carbonaceous R.Conclusions. Combining the criterion of most stable linkage with the MEP concept should greatly reduce the window of potential targets to be searched for in the ISM. Compounds containing the NCO linkage should be preferential targets of future research.

Context. All but one complex organic molecule (COM) detected so far in the interstellar medium (ISM) are achiral; propylene oxide (c-C2H3O)-CH3 is the only exception to this. Finding other chiral species is a priority for astrobiology to progress in the understanding of the emergence of life. Whatever the conditions of their formation, i.e., gas phase or grain chemistry, the detection relies on rotational spectra. This means that, if adsorbed after formation in the gas phase or directly formed on the icy grains, these COMs must escape in the gas phase as free flyers to be detectable. Aims. Learning the lesson drawn from the only observation of a chiral compound and considering the structural constraints imposed to a molecule to be chiral, we look at what species could satisfy these conditions and be potential targets for a radio astronomy search in the ISM gas phase. Methods. This question was addressed by combining two complementary approaches that rely on density functional theory. The structure, energetics, and spectroscopic parameters of each potential candidate were determined using molecular calculations. The propensity for a molecule to remain trapped on the ice coating of the grains was evaluated by numerical simulations making use of a solid state periodic model. Results. Replacing the -CH3 group on rigid propylene oxide by -CN, -CCH, -NH2, -OH, or -HCO gives oxirane daughter molecules whose adsorption energies divide into two classes: below and above the adsorption energy of H2O on solid water-ice ~13.5 kcal mol−1. Conclusions. The best chiral candidate would be a rigid molecule for an easier determination of its radio spectra. This molecule would be composed of a central carbon linked to one hydrogen and three different chemical groups as simple as possible. If not the most stable isomer, this candidate should be as close as possible on the energy scale, possess a significant dipole moment, and be less strongly attached to the ice than H2O itself.

Context. Beyond NH3, only one primary alkylamine, CH3NH2, has been identified in the interstellar medium and the reason why is still not understood: its formation could occur in the gas phase or in icy environments. Aims. To consider any possible difference between the formation of primary and secondary amines, we studied the hydrogenation processes of CH3CN and CH3NC, which would lead to the simple primary CH3CH2NH2 and secondary CH3NHCH3 amines, respectively. Methods. Experimentally, the hydrogenation of CH3CN and CH3NC was carried out under ultra-high vacuum, using two beamlines to inject the nitrile/isonitrile and H onto substrate surfaces of gold or water ice. The reactions were monitored using infrared spectroscopy and the products were followed by mass spectrometry. Theoretically, the energetics of the hydrogenation paths were determined using the M06-2X functional after benchmarking against post Hartree–Fock procedures. Meanwhile, a survey of the high-mass star forming region W51/e2 has been performed. Results. Following co-deposition of CH3CN and H, we show that these species do not react together between 10 and 60 K. For CH3NC we found that the hydrogenation process works all the way through the CH3NHCH3 end product; we also identified the CH3NCH2 intermediate together with side products, CH4 and HCN, showing that the isonitrile backbone is breaking. These results are consistent with the calculations of a high barrier on the first hydrogenation step for CH3CN and a lower barrier for CH3NC. Conclusions. The formation of CH3CH2NH2 by hydrogenation of CH3CN appears rather unlikely in both the gas phase and ice environment whereas that of CH3NHCH3 is a clear possibility. The limiting factor appears to be the efficiency of the tunneling effect through the first activation barrier on the reaction paths. More surveys are required for further insight into the search for amines.

The origin of cometary volatiles remains a major open question in planetary science. Comets may have either agglomerated from crystalline ices condensed in the protosolar nebula (PSN) or from amorphous ice originating from the molecular cloud and interstellar medium. Here, based on the recent argon, krypton, and xenon measurements performed by the ROSINA mass spectrometer on board the European Space Agency's Rosetta spacecraft in the coma of 67P/Churyumov-Gerasimenko, we show that these noble gas relative abundances can be explained if the comet's building blocks formed from a mixture of gas and H2O grains resulting from the annealing of pristine amorphous ice (i.e., originating from the presolar cloud) in the PSN. In this scenario, the different volatiles released during the amorphous-to-crystalline ice phase transition would have been subsequently trapped at lower temperatures in stoichiometric hydrate or clathrate hydrate forms by the crystalline water ice generated by the transition. Once crystalline water was completely consumed by clathration in the similar to 25-80 K temperature range, the volatile species remaining in the gas phase would have formed pure condensates at lower temperatures. The formation of clathrates hydrates and pure condensates to explain the noble gas relative abundances is consistent with a proposed interstellar origin of molecular oxygen detected in 67P/Churyumov-Gerasimenko, and with the measured molecular nitrogen depletion in comets.

Context. Helium, the second most abundant element in the Universe, with a relative abundance of He/H ~ 1/10, has never been observed in any other form than that of a neutral atom (He) or an ion (He+) in the interstellar medium. Since He is a noble gas its non-observation as part of neutral molecular systems is understandable, but it is very surprising for a positively charged species such as HeH+ that is a stable diatomic ion whose spectral signatures are well known in the laboratory. Aims. This non-observation, even in hydrogen rich regions, could imply that HeH+ is not a proper target and that alternatives have to be considered, such as small HeHn+ clusters. The present study aims at finding whether the leading term HeH3+ fulfills the conditions required. Methods. We addressed the question with state-of-the-art numerical simulations. We determined a two-dimension ab initio potential energy surface (PES) of the HeH3+ cluster along the He...H3+ and HeH+...H2 reaction coordinates. The calculations rely on complete active space configuration interaction followed by a second order perturbation treatment (CAS-PT2). This surface was used for the evaluation of the two radiative associations rate constants by means of a quantum treatment of the collision between the interacting fragments. Results. These calculations show unambiguously that HeH3+ is the most stable point on the corresponding global PES. Then, we determined the rate constants of the radiative associations HeH+ + H2 and He + H3+ leading to HeH3+. Conclusions. Significative values were obtained that reach up to 2 × 10-18 cm3 s-1, which should stimulate new tentatives to detect molecular helium in astrophysical objects.

The deficiencies of argon, krypton, and xenon observed in the atmosphere of Titan as well as anticipated in some comets might be related to a scenario of sequestration by H3+ in the gas phase at the early evolution of the solar nebula. The chemical process implied is a radiative association, evaluated as rather efficient in the case of H3+, especially for krypton and xenon. This mechanism of chemical trapping might not be limited to H3+ only, considering that the protonated ions produced in the destruction of H3+ by its main competitors present in the primitive nebula, i.e., H2O, CO, and N2, might also give stable complexes with the noble gases. However the effective efficiency of such processes is still to be proven. Here, the reactivity of the noble gases Ar, Kr, and Xe, with all protonated ions issued from H2O, CO, and N2, expected to be present in the nebula with reasonably high abundances, has been studied with quantum simulation method dynamics included. All of them give stable complexes and the rate coefficients of their radiative associations range from 10−16 to 10−19 cm3 s−1, which is reasonable for such reactions and has to be compared to the rates of 10−16 to 10−18 cm3 s−1, obtained with H3+. We can consider this process as universal for all protonated ions which, if present in the primitive nebula as astrophysical models predict, should act as sequestration agents for all three noble gases with increasing efficiency from Ar to Xe.

S-2 has been observed for decades in comets, including comet 67P/ Churyumov-Gerasimenko. Despite the fact that this molecule appears ubiquitous in these bodies, the nature of its source remains unknown. In this study, we assume that S-2 is formed by irradiation ( photolysis and/ or radiolysis) of S-bearing molecules embedded in the icy grain precursors of comets. and that the cosmic ray flux simultaneously creates voids in ices within which the produced molecules can accumulate. We investigate the stability of S-2 molecules in such cavities, assuming that the surrounding ice is made of H2S or H2O. We show that the stabilization energy of S2 molecules in such voids is close to that of the H2O ice binding energy, implying that they can only leave the icy matrix when this latter sublimates. Because S2 has a short lifetime in the vapor phase, we derive that its formation in grains via irradiation must occur only in low-density environments such as the ISM or the upper layers of the protosolar nebula, where the local temperature is extremely low. In the first case, comets would have agglomerated from icy grains that remained pristine when entering the nebula. In the second case, comets would have agglomerated from icy grains condensed in the protosolar nebula and that would have been efficiently irradiated during their turbulent transport toward the upper layers of the disk. Both scenarios are found consistent with the presence of molecular oxygen in comets.

Context. Almost 20% of the ~200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. Aims. In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. Methods. The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH3CN and CH3NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption in an ultra-high vacuum between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory to represent the organised solid support. Results. The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50% as compared to adsorption on perfect graphene planes. The most stable isomer (CH3CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH3NC), however.

CELINA BERMÚDEZ, L. MARGULÈS, R. A. MOTIYENKO, Laboratoire PhLAM, UMR 8523 CNRS Université Lille 1, Villeneuve d’Ascq, France; BELÉN TERCERO, JOSE CERNICHARO, Molecular Astrophysics, ICMM, Madrid, Spain; J.-C. GUILLEMIN, UMR 6226 CNRS ENSCR, Institut des Sciences Chimiques de Rennes, Rennes, France; Y. ELLINGER, Laboratoire de Chimie Théorique (UMR 7616), Université Paris 6, Paris, FRANCE.

The detection of ArH(+) has revived the interest in the search for noble gas containing species. Despite helium being the second most abundant element in the universe (He/H ∼ 1/10), it has never been observed in any other form than that of a neutral/ionized atom in the interstellar medium. Because He is the "most noble" gas, its non-observation as part of neutral molecular systems is understandable. It is more surprising for charged species, especially HeH(+) whose spectral signatures are well documented in the laboratory. The purpose of this work was to find a simple positive ion containing He, and likely to be observed as an alternative to undetected HeH(+). Among the HeX(2+) diatomics formed with first row atoms, we focused on X = C because of both its relative abundance and the magnitude of its ionization potentials with respect to He. The formation of CHe(2+) by radiative association is the center of this study. The question was addressed by means of numerical simulations using high level ab initio calculations of the CHe(2+) potential surface, followed by a quantum chemical determination of the rate coefficients for the corresponding radiative association in the range of 10 to 1000K. The radiative association path shows a potential well deep enough to accommodate 20 vibrational levels, and no barrier to oppose the reaction. The rate coefficient varies from ∼4.5 × 10(-20) cm(3)s(-1) to ∼2.5 × 10(-22) cm(3)s(-1) for the temperatures considered. The present study suggests that the existence of this species has to be searched for mainly in highly irradiated regions.

ABSTRACT The heavy noble gas deficiencies observed in Titan’s atmosphere and in comets have been proposed to be related to a sequestration process by H 3 + in the gas phase at the early protosolar nebula. Chemical thermodynamics and astrophysics modeling are favorable to this hypothesis, as presented in preceding papers. However, there is a point still to be raised, i.e., that no dynamical study of the efficiency of the collisional processes had been performed so far. Here, we show that, apart from the expected exception of Ne, the rate constants obtained, i.e., 0.7 × 10 −18 , 0.5 × 10 −16 , and 10 −16 (cm 3 s −1 ) for Ar, Kr, and Xe, respectively, are reasonably high for such processes, particularly in the case of Kr and Xe. The temperature dependence is also considered, showing a similar behavior for all noble gases with a peak efficiency in the range 50–60 K. Globally, we can conclude that the scenario of sequestration by H 3 + is definitively comforted by the results of our quantum dynamical treatment. This process may also be responsible of the Ar impoverishment just measured in comet 67P/Churyumov–Gerasimenko by the ROSINA mass spectrometer on board the Rosetta spacecraft.

Context. The results of an observational search for gas phase urea, (NH2)(2)CO toward the Sgr B2-LMH region, have been reported recently. In spite of strong presumptions, whether it is urea or another species (for example an isomer) seems to remain a pending question.Aims. In this note, we consider the energetic aspect of this would-be detection by addressing the relative stabilities of the 22 isomers that can possibly be formed with the CH4N2O set of atoms. By extension, we also consider the 22 sulphur analogues of CH4N2S chemical formula.Methods. The question was first addressed by means of quantum density functional theory (DFT) simulations. The hybrid B3LYP functional was used throughout. The geometries of the 44 molecules part of this survey were fully optimized and verified to be real minima by vibrational analysis. The lowest isomers found this way were then reconsidered in higher level post Hartree-Fock MP2 and coupled cluster CCSD and CCSD(T) calculations to derive more accurate energy differences and dipole moments, whose knowledge is crucial for interpreting micro-and millimetre-wave spectra.Results. We found that urea and thio-urea are the most stable compounds in their respective families. The closest isomers on the energy scale are the iminol tautomeric forms, HN = COH-NH2 and HN = CSH-NH2, whose rotational constants and dipole moments have also been determined.Conclusions. That urea is the lowest energy isomer possibly formed is a strong argument making the detection of this species more than probable. After formamide and acetamide, this result confirms the greatest stability of the -[NH-C=O]-linkage, underlining the interest of the minimum energy criterion as a tool for the primary search of target molecules. Additionally, thio-urea should the analogue to search for.

Molecular oxygen has been detected in the coma of comet 67P/Churyumov-Gerasimenko with abundances in the 1%-10% range by the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis-Double Focusing Mass Spectrometer instrument on board the Rosetta spacecraft. Here we find that the radiolysis of icy grains in low-density environments such as the presolar cloud may induce the production of large amounts of molecular oxygen. We also show that molecular oxygen can be efficiently trapped in clathrates formed in the protosolar nebula (PSN), and that its incorporation as crystalline ice is highly implausible, because this would imply much larger abundances of Ar and N-2 than those observed in the coma. Assuming that radiolysis has been the only O-2 production mechanism at work, we conclude that the formation of comet 67P/Churyumov-Gerasimenko is possible in a dense and early PSN in the framework of two extreme scenarios: (1) agglomeration from pristine amorphous icy grains/particles formed in ISM and (2) agglomeration from clathrates that formed during the disk's cooling. The former scenario is found consistent with the strong correlation between O-2 and H2O observed in comet 67P/Churyumov-Gerasimenko's coma while the latter scenario requires that clathrates formed from ISM icy grains that crystallized when entering the PSN.

Conditions in the protosolar nebula have left their mark in the composition of cometary volatiles, thought to be some of the most pristine material in the solar system. Cometary compositions represent the end point of processing that began in the parent molecular cloud core and continued through the collapse of that core to form the protosun and the solar nebula, and finally during the evolution of the solar nebula itself as the cometary bodies were accreting. Disentangling the effects of the various epochs on the final composition of a comet is complicated. But comets are not the only source of information about the solar nebula. Protostellar disks around young stars similar to the protosun provide a way of investigating the evolution of disks similar to the solar nebula while they are in the process of evolving to form their own solar systems. In this way we can learn about the physical and chemical conditions under which comets formed, and about the types of dynamical processing that shaped the solar system we see today. This paper summarizes some recent contributions to our understanding of both cometary volatiles and the composition, structure and evolution of protostellar disks.