Oxygen fractionation in dense molecular clouds.

We have developed the first gas-grain chemical model for oxygen fractionation (also including sulphur fractionation) in dense molecular clouds, demonstrating that gas-phase chemistry generates variable oxygen fractionation levels, with a particularly strong effect for NO, SO, O2, and SO2. This large effect is due to the efficiency of the neutral 18O + NO, 18O + SO, and 18O + O2 exchange reactions. The modeling results were compared to new and existing observed isotopic ratios in a selection of cold cores. The good agreement between model and observations requires that the gas-phase abundance of neutral oxygen atoms is large in the observed regions. The S16O/S18O ratio is predicted to vary substantially over time showing that it can be used as a sensitive chemical proxy for matter evolution in dense molecular clouds.

The chemistry of disks around T Tauri and Herbig Ae/Be stars.

CONTEXT: Infrared and (sub-)mm observations of disks around T Tauri and Herbig Ae/Be stars point to a chemical differentiation between both types of disks, with a lower detection rate of molecules in disks around hotter stars. AIMS: To investigate the underlying causes of the chemical differentiation indicated by observations we perform a comparative study of the chemistry of T Tauri and Herbig Ae/Be disks. This is one of the first studies to compare chemistry in the outer regions of these two types of disks. METHODS: We developed a model to compute the chemical composition of a generic protoplanetary disk, with particular attention to the photochemistry, and applied it to a T Tauri and a Herbig Ae/Be disk. We compiled cross sections and computed photodissociation and photoionization rates at each location in the disk by solving the FUV radiative transfer in a 1+1D approach using the Meudon PDR code and adopting observed stellar spectra. RESULTS: The warmer disk temperatures and higher ultraviolet flux of Herbig stars compared to T Tauri stars induce some differences in the disk chemistry. In the hot inner regions, H2O, and simple organic molecules like C2H2, HCN, and CH4 are predicted to be very abundant in T Tauri disks and even more in Herbig Ae/Be disks, in contrast with infrared observations that find a much lower detection rate of water and simple organics toward disks around hotter stars. In the outer regions, the model indicates that the molecules typically observed in disks, like HCN, CN, C2H, H2CO, CS, SO, and HCO+, do not have drastic abundance differences between T Tauri and Herbig Ae disks. Some species produced under the action of photochemistry, like C2H and CN, are predicted to have slightly lower abundances around Herbig Ae stars due to a narrowing of the photochemically active layer. Observations indeed suggest that these radicals are somewhat less abundant in Herbig Ae disks, although in any case the inferred abundance differences are small, of a factor of a few at most. A clear chemical differentiation between both types of disks concerns ices. Owing to the warmer temperatures of Herbig Ae disks, one expects snowlines lying farther away from the star and a lower mass of ices compared to T Tauri disks. CONCLUSIONS: The global chemical behavior of T Tauri and Herbig Ae/Be disks is quite similar. The main differences are driven by the warmer temperatures of the latter, which result in a larger reservoir or water and simple organics in the inner regions and a lower mass of ices in the outer disk.

The ESO Diffuse Interstellar Bands Large Exploration Survey: EDIBLES I. Project description, survey sample and quality assessment.

The carriers of the diffuse interstellar bands (DIBs) are largely unidentified molecules ubiquitously present in the interstellar medium (ISM). After decades of study, two strong and possibly three weak near-infrared DIBs have recently been attributed to the [Formula: see text] fullerene based on observational and laboratory measurements. There is great promise for the identification of the over 400 other known DIBs, as this result could provide chemical hints towards other possible carriers. In an effort to systematically study the properties of the DIB carriers, we have initiated a new large-scale observational survey: the ESO Diffuse Interstellar Bands Large Exploration Survey (EDIBLES). The main objective is to build on and extend existing DIB surveys to make a major step forward in characterising the physical and chemical conditions for a statistically significant sample of interstellar lines-of-sight, with the goal to reverse-engineer key molecular properties of the DIB carriers. EDIBLES is a filler Large Programme using the Ultraviolet and Visual Echelle Spectrograph at the Very Large Telescope at Paranal, Chile. It is designed to provide an observationally unbiased view of the presence and behaviour of the DIBs towards early-spectral type stars whose lines-of-sight probe the diffuse-to-translucent ISM. Such a complete dataset will provide a deep census of the atomic and molecular content, physical conditions, chemical abundances and elemental depletion levels for each sightline. Achieving these goals requires a homogeneous set of high-quality data in terms of resolution (R ~ 70 000 - 100 000), sensitivity (S/N up to 1000 per resolution element), and spectral coverage (305-1042 nm), as well as a large sample size (100+ sightlines). In this first paper the goals, objectives and methodology of the EDIBLES programme are described and an initial assessment of the data is provided.

Chemical complexity in the horsehead photodissociation region.

The interstellar medium is known to be chemically complex. Organic molecules with up to 11 atoms have been detected in the interstellar medium, and are believed to be formed on the ices around dust grains. The ices can be released into the gas-phase either through thermal desorption, when a newly formed star heats the medium around it and completely evaporates the ices; or through non-thermal desorption mechanisms, such as photodesorption, when a single far-UV photon releases only a few molecules from the ices. The first mechanism dominates in hot cores, hot corinos and strongly UV-illuminated PDRs, while the second dominates in colder regions, such as low UV-field PDRs. This is the case of the Horsehead were dust temperatures are approximately eual to 20-30 K, and therefore offers a clean environment to investigate the role of photodesorption. We have carried out an unbiased spectral line survey at 3, 2 and 1mm with the IRAM-30m telescope in the Horsehead nebula, with an unprecedented combination of bandwidth, high spectral resolution and sensitivity. Two positions were observed: the warm PDR and a cold condensation shielded from the UV field (dense core), located just behind the PDR edge. We summarize our recently published results from this survey and present the first detection of the complex organic molecules HCOOH, CH2CO, CH3CHO and CH3CCH in a PDR. These species together with CH3CN present enhanced abundances in the PDR compared to the dense core. This suggests that photodesorption is an efficient mechanism to release complex molecules into the gas-phase in far-UV illuminated regions.

Determination of the ortho to para ratio of H2Cl+ and H2O+ from submillimeter observations.

The opening of the submillimeter sky with the Herschel Space Observatory has led to the detection of new interstellar molecular ions, H2O(+), H2Cl(+), and HCl(+), which are important intermediates in the synthesis of water vapor and hydrogen chloride. In this paper, we report new observations of H2O(+) and H2Cl(+) performed with both Herschel and ground-based telescopes, to determine the abundances of their ortho and para forms separately and derive the ortho-to-para ratio. At the achieved signal-to-noise ratio, the observations are consistent with an ortho-to-para ratios of 3 for both H2O(+) and H2Cl(+), in all velocity components detected along the lines-of-sight to the massive star-forming regions W31C and W49N. We discuss the mechanisms that contribute to establishing the observed ortho-to-para ratio and point to the need for a better understanding of chemical reactions, which are important for establishing the H2O(+) and H2Cl(+) ortho-to-para ratios.

Models of H3+ in warm, diffuse, molecular gas in the Galactic centre.

Oka et al. (Oka et al. 2005 Astrophys. J. 632, 882-893) have recently observed a large column density of H3+ in the Galactic centre. In one of the gaseous components, a column density of H3+ in its metastable level (3,3) of approximately 4 x 10(14) cm(-2) is measured. From the excitation of H3+, they deduce a density below 50 cm(-3) and a temperature approximately 270 K. In this paper, we report results for this region from a new version of our PDR code which includes the H3+ excitation. Models show it is unlikely that the mean temperature of the gas could be above 100 K. We also show that there is a possibility to produce hot H3+ in C-shocks.