Les glaces du milieu interstellaire sont invoquées comme l'une des origines de la formation de molécules organiques complexes dans l'espace. En effet, elles constituent un support catalytique pour des réactions chimiques et pourraient ainsi expliquer la formation de molécules d'intérêt prébiotique. Toutefois, en raison de la faible température des milieux considérés, la vitesse de la réaction est contrainte par le déplacement des différentes réactifs l'un vers l'autre. L'objectif de cette thèse est donc de traiter la réactivité et la diffusion de molécules simples dans les glaces interstellaires. Je présente dans cette thèse les résultats de l'étude de la réaction entre le dioxyde de carbone et l'ammoniac dans les glaces interstellaires. Cette étude a été effectuée au Laboratoire Univers et Particules de Montpellier ; elle combine différentes méthodes de la chimie théorique et confronte les résultats avec ceux issus d'expériences que j'ai réalisées au Laboratoire de Physique des interactions Ioniques et Moléculaires de l'Université d'Aix-Marseille. Dans une première partie, des simulations de dynamique moléculaire classiques sont employées pour simuler un modèle de glace amorphe basse densité. Ce modèle est utilisé pour simuler la trajectoire de petites molécules (NH3, CO, CO2, H2CO) dans cette glace et en déduire des coefficients de diffusion à différentes températures. Ces résultats sont comparés à des résultats expérimentaux de diffusion du dioxyde de carbone ce qui valide la méthode théorique utilisée et permet de suggérer un mécanisme pour ce processus de diffusion. Dans une deuxième partie, la réaction entre le dioxyde de carbone et l'ammoniac est traitée dans le cadre de la théorie de la fonctionnelle densité par une approche « super-molécule ». Dans cette approche, le profil d'énergie et le mécanisme de la réaction dans des complexes moléculaires xNH3:CO2:yH2O sont étudiés. Deux produits de la réaction sont localisés : le carbamate d'ammonium et l'acide carbamique. La barrière d'énergie de la réaction obtenue est similaire à celle obtenue expérimentalement, et le carbamate d'ammonium est confirmé comme produit majoritaire de la réaction. Le profil d'énergie obtenu par cette approche « super-molécule » est ensuite étudié par dynamique moléculaire ab initio contrainte et le profil d'énergie libre est calculé par la méthode d'Intégration Thermodynamique. Cette approche confirme la forme générale du profil d'énergie et met en évidence un fort effet entropique du réseau d'eau. Je dresse finalement des conclusions sur les plans méthodologiques et astrochimiques permettant d'inscrire ma thèse dans des perspectives futures, notamment en incluant les barrières d'énergie de diffusion et de réaction, dans des modèles astrochimiques prenant en compte directement les réactions chimiques dans les glaces interstellaires. / It is postulated nowadays that complex organic molecules in space form on the surface and in the volume of interstellar ices. These ices can catalyse chemical reactions what could explain the formation of prebiotic molecules. However, because of the low temperatures, the diffusion of the reactants one towards another is slow, limiting their reactivity. The objectif of this thesis is to treat the reactivity and the diffusion of simple molecules in interstellar ices. I present in this thesis the results of the study of the chemical reaction between carbon dioxide and ammonia in interstellar ices. This study was conducted in the Laboratoire Univers et Particules de Montpellier : it combines various theoretical chemistry methods and confront the results to experimental ones I participated in at the Laboratoire de Physique des Interactions Ioniques etMoléculaires of the Aix-Marseille university. In a first part, classical molecular dynamic simulations are used to simulate a low-density amorphous ice model and to calculate the diffusion coefficients at various temperatures of a series of small molecules (NH3, CO, CO2, H2CO). These results are compared to the experimental diffusion coeficients of the carbon dioxide validating the theoretical approach used and allowing to porpose a mechanism for the diffusion process. In a second part, the reaction between carbon dioxide and ammonia is studied in the frame of Density-Functional Theory using a « super-molecular » approach. In this approach, the reaction energy profile for the molecular complexes xNH3:CO2:yH2O, is studied. Two reaction products are localised : the ammonium carbamate and the carbamic acid. The reaction energy barrier obtained by these calculations is similar to the one obtained experimentally, and the ammonium carbamate is confirmed as the major reaction product. The obtained energy profile is therfore investigated by constrained ab initio molecular dynamics and the free energy profile is computed with the Thermodynamics Integration method. These calculations confirme the general form of the previous energy profile and enlight the strong entropic effect of the water network. Finally, conclusions are drawn, and perspectives on methodological as well as on astrochemical aspects, as the inclusion of the reaction and diffusion energy barriers I calculated in astrochemical models, are given.

Orientador: Carmen Maria Andreazza / Banca: Edson Denis Leonel / Banca: José Williams dos Santos Vilas Boas / Resumo: De acordo com os resultados observacionais de condensações de nuvens moleculares escuras, grandes variações na razão 13CO/C18O são observadas quando se comparam os resultados obtidos nas condensações situadas dentro da mesma nuvem, bem como de nuvem para nuvem. O valor médio dessa razão na condensação principal de Ophiuchus é inferior a 5. Por outro lado, o valor encontrado nas condensações que estão situadas ao norte de Oph é maior que 10. Grandes diferenças também são encontradas quando se comparam os resultados observacionais de diferentes nuvens escuras, tais como Ophiuchus e Taurus, onde são observados também um decréscimo da razão C18O/C17O com o aumento da densidade. Os processos químicos e físicos que governam essas variações ainda não estão claros. Nesse sentido, o objetivo da presente proposta é analisar a influência do colapso gravitacional de condensações de nuvens moleculares escuras na síntese das moléculas CO, C17O, C18O, 13CO, 13C17O e 13C18O. Tal análise é feita com base em comparações entre modelos que consideram diferentes condições entre si, tais como, tamanho da cadeia química, velocidade de colapso, densidade inicial e processos de congelamento de espécies químicas na superfície de grãos de poeira. Os resultados obtidos mostram que o tamanho da cadeia química tem influência nas razões 13CO/C18O e C18O/C17O, mas não tanto quanto a densidade inicial e a velocidade do colapso. Além disso, o congelamento das espécies químicas nos grãos é mais significativo nos estágios mais avançados da evolução da condensação. Os modelos de condensações escuras que sofrem colapso gravitacional lento e em queda livre reproduzem satisfatoriamente as razões 13CO/C18O e C18O/C17O observadas, o que permite concluir que o colapso gravitacional pode ter um importante efeito nas referidas razões. / Abstract: According to the observational results of dark molecular clouds condensations, large variations in the ratio 13CO/C18O are observed when comparing the results obtained in the condensations located within the same cloud and cloud to cloud. The average value of this ratio in the main condensation of Ophiuchus is below 5. On the other hand, the value found in the condensations that are located north of Oph is larger than 10. Large differences are also found when comparing the observational results of different dark clouds such as Ophiuchus and Taurus, in which are also found a decrease of the C18O/C17O ratio with increasing density. The chemical and physical processes that govern these variations are still unclear. In this sense, the objective of this proposal is to analyze the influence of the gravitational collapse of centrally condensed clumps of dense molecular gas in the synthesis of the CO, C17O, C18O, 13CO, 13C17O and 13C18O molecules. This analysis is based on comparisons among models that consider different condition, such as, chemical chain, initial density, speed of collapse and freezing processes of the chemical species on the surface of dust grains. The results show that the size of the chemical chain has influence on the 13CO/C18O and C18O/C17O ratios, but they are not as important as the initial density and the speed of the collapse. Furthermore, the freezing of chemical species on the grains occurs at later times of the collapse. The models of a gravitational free-fall collapsing core and of slowly contracting core with higher initial density are consistent with observations. These results indicate that the gravitational collapse of molecular cores can have an important effect in the 13CO/C18O and C18O/C17O ratios. / Mestre

La naissance des étoiles massives est aujourd’hui encore mal comprise. En particulier, les conditions initiales de leur formation restent largement inconnues. Pour éclairer cette question, nous avons réalisé un relevé spectral complet non biaisé avec le télescope 30 m de l’IRAM vers la protoétoile massive CygX-N63 (M ~ 58 M◦ et L~ 340 L◦). Nous avons mis en évidence une complexité moléculaire significative avec plus de 40 espèces. L’ion CF+ est observé pour la première fois dans une protoétoile. Une possible première détection de l’espèce prébiotique CH2NH dans une protoétoile est aussi proposée, ainsi qu’une première détection de DOCO+. Cette étude spectroscopique, accompagnée d’observations interférométriques avec le Plateau de Bure, permet de séparer la contribution des différentes régions : enveloppe froide, région tiède, région de type hot core et flot bipolaire. L’enveloppe est constituée d’une grande quantité de gaz froid peu évolué, offrant un potentiel important pour la compréhension des phases précoces de la formation stellaire massive et compatible avec un scénario d’effondrement monolithique. La modélisation chimique montre que la chimie de ce gaz est encore hors équilibre, malgré sa haute densité, et confirme la jeunesse de la protoétoile avec un âge chimique de seulement ~ 1000 ans. N63 est un précurseur de hot core plutôt qu’un hot corino massif. Il serait donc possible de distinguer, grâce à des diagnostics chimiques évolutifs, les précurseurs d’étoiles massives des protoétoiles de masse faible ou ntermédiaire. / High-mass star formation is still poorly understood. In particular the initial conditions of their formation are unknown. To explore this question, a complete unbiased spectral survey was conducted with the IRAM 30 m telescope toward the massive protostar CygX-N63 (M~58 M◦ and L~ 340 L◦). A significant molecular complexity is found, with more than 40 species. The ion CF+ is observed for the first time in a protostar. A possible first detection of the prebiotic species CH2NH in a protostar and a first detection of DOCO+ are proposed. This spectroscopic study, along with Plateau de Bure interferometric observations, allows us to separate the contribution of different regions : cold envelope, lukewarm region, hot corelike region and outflow. The envelope contains large amounts of cold and young gas, which gives us the opportunity to better understand the early phases of massive star formation. The chemical modeling shows that the chemistry is still out of equilibrium, despite its high density, and confirms the youth of the protostar with a chemical age of ~ 1000 years. N63 is a hot core precursor rather than a massive hot corino. The use of chemical diagnostics of the evolution would then allow to distinguish massive star precursors from low-mass or intermediate-mass protostars.

Les étoiles de masse intermédiaire (2M⊙ ≤ M ≤ 10M⊙) sont parmi les sources dominantes du champ interstellaire FUV dans la Galaxie. Elles régulent les phases du milieu interstellaire et l’ensemble des processus de formation stellaire galactique. Alors que les protoétoiles de type solaire et massives ont été et continuent à faire l’objet de nombreuses études, la formation des étoiles intermédiaires a été relativement peu étudiée. Leur structure physique, composition chimique et leur richesse moléculaire sont un domaine à explorer.L’objectif de ma thèse est d’obtenir un recensement détaillé et aussi complète que possible des propriétés physico-chimiques d’une protoétoile isolée de masse intermédiaire. Notre choix s’est porté sur Cep E-mm (100 L⊙).J’ai pour cela complété un relevé spectral de l’émission moléculaire dans les bandes (sub)millimétriques entre 72 et 350 GHz avec le télescope de 30m de l’IRAM. La sensibilité des observations a permis d’identifier la présence de nombreuses molécules complexes organiques (COMs) dans l’enveloppe de la protoétoile, mais aussi, plusieurs espèces moléculaires inhabituelles dans le jet généré par la protoétoile. Des observations complémentaires avec le télescope de 30m ont permis de cartographier l’émission moléculaire à grande échelle (20’’ à 11’’ ; 15000 à 8000 UA). En parallèle, des cartes interférométriques de l’émission moléculaire entre 86 – 90 GHz et 216 – 220 GHz ont été obtenues avec l’interféromètre de l’IRAM (NOEMA) à 1.4’’ (1000 UA) de résolution angulaire. Ces observations m’ont permis d’obtenir une première description de la distribution de l’émission moléculaire au sein de l’enveloppe, des grandes échelles, dans les parties extérieures de l’enveloppe étendue, aux petites échelles dans la région d’un hot corino. Les études présentées ici ont suivi un travail méticuleux de réduction et d’analyse des données, single-dish et interférométriques. Plus précisément, j’ai identifié et séparé les contributions à l’émission détectée dans le lobe du télescope de 30m de l’IRAM des différentes régions physiques du cœur protostellaire. De ce fait, j’ai identifié et caractérisé quatre composantes physiques qui diffèrent par leurs propriétés spectroscopiques et leurs conditions d’excitation : l’enveloppe étendue, le hot corino, le flot bipolaire basse vitesse et le jet à haute vitesse. Enfin, l’anisotropie de la distribution de brillance du flot et du jet bipolaire ne peut pas être modélisée par l’approche ‘’classique’’ d’une source gaussienne. J’ai développé des outils spécifiques semi-analytiques pour calculer de manière approchée, et plus raisonnable, le couplage entre le lobe du télescope et la source. / Intermediate-mass stars (2 M⊙ ≤ M ≤ 10 M⊙) are among the dominant sources of FUV interstellar field in the Galaxy. They regulate the phases of interstellar medium and the whole process of galactic star formation. While solar-type and massive protostars have been and continue to be the subject of many studies, the formation of intermediate stars has been relatively little studied. Their physical structure, chemical composition and molecular richness are still a subject to explore.The aim of my thesis is to obtain a detailed census, as complete as possible ,of the physical and chemical structure of an isolated intermediate-mass protostar: Cep E-mm (100 L⊙).I have completed a spectral survey of the molecular emission in the (sub)millimetre bands between 72 and 350 GHz with IRAM 30m telescope. The sensitivity of the observations made it possible to identify the presence of numerous complex organic molecules (COMs) in the protostar envelope, but also several unusual molecular species in the protostellar jet. Additionally, further observations with the IRAM 30m telescope made it possible to map the molecular emission at large scale (20’’ to 11’’; 15000 to 8000 AU). In parallel, interferometric maps of the molecular emission between 86 – 90 GHz and 216 – 220 GHz were obtained with NOEMA, the IRAM interferometer, at 1.4’’ (1000 AU) of angular resolution. These observations allowed me to obtain the distribution of molecular emission within the source, from large scales in the outer parts of the extended envelope, to the small scales in the hot corino region. The single-dish and interferometric observations were reduced and analysed in a meticulous manner. More precisely, I identified and separated the molecular emission contribution from the different physical regions as observed with the IRAM 30m telescope. I have identified and characterized fours physical components that differ in their spectroscopic properties and excitation conditions: the extended envelope, the hot corino, the bipolar outflow and the high-velocity jet. Finally, the anisotropy of the brightness distribution from the outflow system cannot be modelled by the “classical” Gaussian approach. I have developed specific tools to estimate, in a semi-analytical manner, the coupling between the telescope lobe and the source.

Spectroscopic observations of cold and dense interstellar clouds show the presence of "dirty ice" mantles on dust grains, mainly composed by water molecules. These ices are enriched by the presence of other simple species that are either formed by surface reactions or accreted from the gas phase. While there is quite a general consensus that interstellar water ice is mainly amorphous, its morphology (porous or compact) still remains poorly known. Morphology is important due to its influence both on the catalytic efficiency of grain surfaces and on the release to the grain of the fraction of the formation energy of species, as shown by laboratory simulations of molecular hydrogen formation. Ice porosity may be identified through the weak infrared absorption features (~ 2.7 μm) showing the presence of dangling bonds on the pore surface. To our knowledge, there has been to date no detection of such absorptions in the infrared spectra of interstellar ices, perhaps suggesting that they may have a compact nature. It has been already investigated that interstellar porous ice may be compacted by the transient heating of stellar radiation and cosmic ray bombardment. In this thesis I report an experimental work, performed using FORMOLISM (the experimental apparatus at the University of Cergy-Pontoise - France), that shows relevant changes in the ice morphology following atomic hydrogen exposure. In particular, it is shown that a thin highly porous ice film is gradually changed into a more compact structure. This is probably due to the transient heating caused by the energy released to the ice during H2 formation. Such a process may also produce in the interstellar space compact amorphous ice mantles concurrently with the other envisaged processes. Moreover, I have experimentally analyzed the morphology of the just formed water ice. Analysing one of the possible mechanism of water formation (the pathway H + O2) under conditions mimicking those found in a molecular cloud, we have found that the water just synthesized has a non-porous structure. Indeed, the layers of water formed in this way show the kinetic characteristics typical of a compact (non-porous) ice, as for instance the D2 TPD peak position.

Le but de la présente thèse est l'étude de la compléxité moléculaire dans les régions de formation stellaires. Cette thèse s'axe sur deux classes de molécule aux caractéristiques prébiotiques : les molécules organiques complexes et les cyanopolyynes.Dans ce contexte, j'ai analysé des données d'un seul échantillon de relevés spec- traux en exploitant des codes de transfert radiatif à l'équilibre thermodynamique local (LTE) et/ou non-LTE pour deux sources : une proto-étoile de type solaire dans un environnement calme (IRAS 16293-2422) et un proto-ama constitué de proto-étoile de type solaire (OMC2-FIR4).L'objectif est de trouver des similar- ités et des différences entre ces deux cas.J'ai utilisé des données issu de deux relevés spectraux : TIMASSS (The IRAS16293-2422 Millimeter And Submilimeter Spectral Survey) réalisés en 2011 (Caux et al. 2011), et ASAI(Astrochemical Surveys At IRAM) réalisés pen- dant la période 2013-2015 (eg Lopez-Sepulcre et al.2015). J'ai extrais les lignes (identification et intensité intégrée) en utilisant le paquet disponible publique- ment : CASSIS (Centre d'Analyse Scientifique de Spectres Infrarouges et Sub- millimetrique). Pour finir, j'ai utilisé le paquet GRAPES (GRenoble Analysis of Protostellar Envelope Spectral) afin de modéliser la distribution spectrale énergétique de ligne (SLED) des molécules détectées, mais aussi afin d'estimer leurs abondances à travers l'envelope de IRAS16293 et du coeur chaud OMC2- FIR4.Les principaux résultats de la thèse sont :1. Le premier recensement complet des molecules organiques complexes (COMs) dans IRAS162932. La première détéction de COMs dans l'enveloppe froide d'une proto-étoile de type solaire (IRAS16293-2422) supportant l'idée qu'un méchanisme de formation, relativement efficace pour les COMs détectées, doit exister en phase gazeuse froide.3. La découverte d'une fine corrélation entre le diméthyle-éther (DME) et le méthyle-formate (MF) suggère une relation mère fille entre ces deux espèces.4. La detection de formamide, espèce avec un très fort potentiel prébiotique, dans plusieurs protoétoiles incluant IRAS16293-2422 et OMC2-FIR4.5. Le recensement complet des cyanopolyynes dans IRAS16293 et OMC2- FIR4 avec la détection de HC3N, HC5N, DC3N et pour OMC2-FIR4: le C13 isotopologue du HC3N cyanopolyynes.Ces résultats sont le sujet principal de deux publications (Jaber et al.2014, ApJ; Lopez-Sepulcre, Jaber et al.2015,MNRAS), un article accepté (Jaber et al., A & A) et un article à soumettre (Jaber et al. A & A). / The present PhD thesis goal is the study of the molecular complexity in solar type star forming regions. It specifically focuses on two classes of molecules with a pre-biotic value, the complex organic molecules and the cyanopolyynes.At this scope, I analyzed data from single-dish spectral surveys by means of non-LTE or/and non-LTE radiative transfer codes in two sources, a solar type protostar in an isolated and quiet environment (IRAS16293-2422) and a proto-cluster of solar type protostars (OMC2-FIR4). The goal is to find similarities and differences between these two cases.I used data from two spectra surveys: TIMASSS (The IRAS16293-2422 Millimeter And Submillimeter Spectral Survey), which has been carried out in 2011 (Caux et al. 2011), and ASAI (Astrochemical Surveys At IRAM), which has been carried out in 2013-2015 (e.g. Lopez-Sepulcre et al. 2015).I extracted the lines (identification and integrated intensity) by means of the publicly available package CASSIS (Centre dAnalyse Scientifique de Spectres Infrarouges et Submillimtriques).Finally, I used the package GRAPES (GRenoble Analysis of Protostellar Envelope Spectra) to model the Spectral Line Energy Distribution (SLED) of the detected molecules, and to estimate their abundance across the envelope and hot corino of IRAS16293-2422 and OMC2-FIR4, respectively.The major results of the thesis are:1) The first full census of complex organic molecules (COMs) in IRAS16293-2422;2) The first detection of COMs in the cold envelope of a solar type protostar (IRAS16293-2422), supporting the idea that a relatively efficient formation mechanism for the detected COMs must exist in the cold gas phase;3) The discovery of a tight correlation between the dimethyl ether (DME) and methyl format (MF), suggesting a mother-daughter relationship;4) The detection of formamide, a species with a very high pre-biotic value, in several protostars, included IRAS16293-2422 and OMC2-FIR4;5) The full census of the cyanopolyynes in IRAS16293-2422 and OMC2-FIR4, with the detection of HC3N and HC5N, DC3N and, for OMC2-FIR4, the 13C isotopologue of HC3N cyanopolyynes.These results are the focus of two published articles (Jaber et al. 2014, ApJ; Lopez-Sepulcre, Jaber et al. 2015, MNRAS), one accepted article (Jaber et al., A&A) and a final article to be submitted (Jaber et al., A&A).

This work is focused on laboratory studies of ion chemistry at conditions relevant for astrophysics. The three main outcomes of the thesis are: (1) The experimental study of the reaction rate coefficient of the associative detachment reaction H- + H -> H2 + e-; measurement of the thermal rate coefficient at the temperatures in the range 10-135 K is described. (2) The design of a novel apparatus for detecting the electrons produced in the RF trap and measuring their energy; numerical simulations and preliminary experimental results are presented. (3) The development of a model of the electron cooling in the afterglow plasma and the application of the model in the analysis of the H3+ recombination measurements.

Made available in DSpace on 2014-06-11T19:25:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-12-21Bitstream added on 2014-06-13T19:53:20Z : No. of bitstreams: 1 vichietti_rm_me_rcla.pdf: 842604 bytes, checksum: 731ca276a75c1b92840e57bd7497b5e1 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / De acordo com os resultados observacionais de condensações de nuvens moleculares escuras, grandes variações na razão 13CO/C18O são observadas quando se comparam os resultados obtidos nas condensações situadas dentro da mesma nuvem, bem como de nuvem para nuvem. O valor médio dessa razão na condensação principal de Ophiuchus é inferior a 5. Por outro lado, o valor encontrado nas condensações que estão situadas ao norte de Oph é maior que 10. Grandes diferenças também são encontradas quando se comparam os resultados observacionais de diferentes nuvens escuras, tais como Ophiuchus e Taurus, onde são observados também um decréscimo da razão C18O/C17O com o aumento da densidade. Os processos químicos e físicos que governam essas variações ainda não estão claros. Nesse sentido, o objetivo da presente proposta é analisar a influência do colapso gravitacional de condensações de nuvens moleculares escuras na síntese das moléculas CO, C17O, C18O, 13CO, 13C17O e 13C18O. Tal análise é feita com base em comparações entre modelos que consideram diferentes condições entre si, tais como, tamanho da cadeia química, velocidade de colapso, densidade inicial e processos de congelamento de espécies químicas na superfície de grãos de poeira. Os resultados obtidos mostram que o tamanho da cadeia química tem influência nas razões 13CO/C18O e C18O/C17O, mas não tanto quanto a densidade inicial e a velocidade do colapso. Além disso, o congelamento das espécies químicas nos grãos é mais significativo nos estágios mais avançados da evolução da condensação. Os modelos de condensações escuras que sofrem colapso gravitacional lento e em queda livre reproduzem satisfatoriamente as razões 13CO/C18O e C18O/C17O observadas, o que permite concluir que o colapso gravitacional pode ter um importante efeito nas referidas razões. / According to the observational results of dark molecular clouds condensations, large variations in the ratio 13CO/C18O are observed when comparing the results obtained in the condensations located within the same cloud and cloud to cloud. The average value of this ratio in the main condensation of Ophiuchus is below 5. On the other hand, the value found in the condensations that are located north of Oph is larger than 10. Large differences are also found when comparing the observational results of different dark clouds such as Ophiuchus and Taurus, in which are also found a decrease of the C18O/C17O ratio with increasing density. The chemical and physical processes that govern these variations are still unclear. In this sense, the objective of this proposal is to analyze the influence of the gravitational collapse of centrally condensed clumps of dense molecular gas in the synthesis of the CO, C17O, C18O, 13CO, 13C17O and 13C18O molecules. This analysis is based on comparisons among models that consider different condition, such as, chemical chain, initial density, speed of collapse and freezing processes of the chemical species on the surface of dust grains. The results show that the size of the chemical chain has influence on the 13CO/C18O and C18O/C17O ratios, but they are not as important as the initial density and the speed of the collapse. Furthermore, the freezing of chemical species on the grains occurs at later times of the collapse. The models of a gravitational free-fall collapsing core and of slowly contracting core with higher initial density are consistent with observations. These results indicate that the gravitational collapse of molecular cores can have an important effect in the 13CO/C18O and C18O/C17O ratios.

A study has been conducted of 12C/13C ratios in five complex molecules in the Galactic center. H2CS, CH3CCH, NH2CHO, CH2CHCN, and CH3CH2CN and their 13C-substituted species have been observed in numerous transitions at 1, 2, and 3 mm, acquired in a spectral-line survey of Sgr B2(N), conducted with the telescopes of the Arizona Radio Observatory (ARO). Between 22 and 54 individual, unblended lines for the 12C species and 2–54 for 13C-substituted analogs were modeled in a global radiative transfer analysis. All five molecules were found to consistently exhibit two velocity components near VLSR ∼ 64 and 73 km s−1, with column densities ranging from Ntot ∼ 3 × 1014 − 4 × 1017 cm−2 and ∼2 × 1013 − 1 × 1017 cm−2 for the 12C and 13C species, respectively. Based on 14 different isotopic combinations, ratios were obtained in the range 12C/13C = 15 ± 5 to 33 ± 13, with an average value of 24 ± 7, based on comparison of column densities. These measurements better anchor the 12C/13C ratio at the Galactic center, and suggest a slightly revised isotope gradient of 12C/13C = 5.21(0.52) DGC + 22.6(3.3). As indicated by the column densities, no preferential 13C enrichment was found on the differing carbon sites of CH3CCH, CH2CHCN, and CH3CH2CN. Because of the elevated temperatures in Sgr B2(N), 13C isotopic substitution is effectively “scrambled,” diminishing chemical fractionation effects. The resulting ratios thus reflect stellar nucleosynthesis and Galactic chemical evolution, as is likely the case for most warm clouds.

Context. At the end of their lives, most stars lose a significant amount of mass through a stellar wind. The specific physical and chemical circumstances that lead to the onset of the stellar wind for cool luminous stars are not yet understood. Complex geometrical morphologies in the circumstellar envelopes prove that various dynamical and chemical processes are interlocked and that their relative contributions are not easy to disentangle. Aims. We aim to study the inner-wind structure (R < 250 R-star) of the well-known red supergiant VY CMa, the archetype for the class of luminous red supergiant stars experiencing high mass loss. Specifically, the objective is to unravel the density structure in the inner envelope and to examine the chemical interaction between gas and dust species. Methods. We analyse high spatial resolution (similar to 0 ''.024 x 0 ''.13) ALMA science verification (SV) data in band 7, in which four thermal emission lines of gaseous sodium chloride (NaCl) are present at high signal-to-noise ratio. Results. For the first time, the NaCl emission in the inner wind region of VY CMa is spatially resolved. The ALMA observations reveal the contribution of up to four different spatial regions. The NaCl emission pattern is different compared to the dust continuum and TiO2 emission already analysed from the ALMA SV data. The emission can be reconciled with an axisymmetric geometry, where the lower density polar/rotation axis has a position angle of similar to 50 degrees measured from north to east. However, this picture cannot capture the full morphological diversity, and discrete mass ejection events need to be invoked to explain localized higher-density regions. The velocity traced by the gaseous NaCl line profiles is significantly lower than the average wind terminal velocity, and much slower than some of the fastest mass ejections, signalling a wide range of characteristic speeds for the mass loss. Gaseous NaCl is detected far beyond the main dust condensation region. Realising the refractory nature of this metal halide, this hints at a chemical process that prevents all NaCl from condensing onto dust grains. We show that in the case of the ratio of the surface binding temperature to the grain temperature being similar to 50, only some 10% of NaCl remains in gaseous form while, for lower values of this ratio, thermal desorption efficiently evaporates NaCl. Photodesorption by stellar photons does not seem to be a viable explanation for the detection of gaseous NaCl at 220 R-star from the central star, so instead, we propose shock-induced sputtering driven by localized mass ejection events as an alternative. Conclusions. The analysis of the NaCl lines demonstrates the capabilities of ALMA to decode the geometric morphologies and chemical pathways prevailing in the winds of evolved stars. These early ALMA results prove that the envelopes surrounding evolved stars are far from homogeneous, and that a variety of dynamical and chemical processes dictate the wind structure.