Aims. We present a new version of the UMIST Database for Astrochemistry, the fourth such version to be released to the public. The current version contains some 4573 binary gas-phase reactions, an increase of 10% from the previous (1999) version, among 420 species, of which 23 are new to the database. Methods. Major updates have been made to ion-neutral reactions, neutral-neutral reactions, particularly at low temperature, and dissociative recombination reactions. We have included for the first time the interstellar chemistry of fluorine. In addition to the usual database, we have also released a reaction set in which the effects of dipole-enhanced ion-neutral rate coefficients are included. Results. These two reactions sets have been used in a dark cloud model and the results of these models are presented and discussed briefly. The database and associated software are available on the World Wide Web at www.udfa.net.

Context. The atmosphere of hot Jupiters can be probed by primary transit and secondary eclipse spectroscopy. Owing to the intense UV irradiation, mixing, and circulation, their chemical composition is maintained out of equilibrium and must be modeled with kinetic models. Aims. Our purpose is to release a chemical network and the associated rate coefficients, developed for the temperature and pressure range relevant to hot Jupiters atmospheres. Using this network, we study the vertical atmospheric composition of the two hot Jupiters (HD 209458b and HD 189733b) with a model that includes photolyses and vertical mixing, and we produce synthetic spectra. Methods. The chemical scheme has been derived from applied combustion models that were methodically validated over a range of temperatures and pressures typical of the atmospheric layers influencing the observations of hot Jupiters. We compared the predictions obtained from this scheme with equilibrium calculations, with different schemes available in the literature that contain N-bearing species, and with previously published photochemical models. Results. Compared to other chemical schemes that were not subjected to the same systematic validation, we find significant differences whenever nonequilibrium processes take place (photodissociations or vertical mixing). The deviations from the equilibrium, hence the sensitivity to the network, are larger for HD 189733b, since we assume a cooler atmosphere than for HD 209458b. We found that the abundances of NH 3 and HCN can vary by two orders of magnitude depending on the network, demonstrating the importance of comprehensive experimental validation. A spectral feature of NH 3 at 10.5 μm is sensitive to these abundance variations and thus to the chemical scheme.Conclusions. Due to the influence of the kinetics, we recommend using a validated scheme to model the chemistry of exoplanet atmospheres. The network we release is robust for temperatures within 300-2500 K and pressures from 10 mbar up to a few hundred bars, for species made of C, H, O, and N. It is validated for species up to 2 carbon atoms and for the main nitrogen species (NH 3 , HCN, N 2 , NO x ). Although the influence of the kinetic scheme on the hot Jupiters spectra remains within the current observational error bars (with the exception of NH 3 ), it will become more important for atmospheres that are cooler or subjected to higher UV fluxes, because they depart more from equilibrium.

Context. The inner layers of circumstellar envelopes around asymptotic giant branch stars are sites where a variety of processes such as thermochemical equilibrium, shocks induced by the stellar pulsation, and condensation of dust grains determine the chemical composition of the material that is expelled into the outer envelope layers and, ultimately, into interstellar space. Aims. We aim at studying the abundances, throughout the whole circumstellar envelope of the carbon star IRC +10216, of several molecules formed in the inner layers in order to constrain the different processes at work in such regions. Methods. Observations towards IRC +10216 of CS, SiO, SiS, NaCl, KCl, AlCl, AlF, and NaCN have been carried out with the IRAM 30-m telescope in the 80−357.5 GHz frequency range. A large number of rotational transitions covering a wide range of energy levels, including highly excited vibrational states, are detected in emission and serve to trace different regions of the envelope. Radiative transfer calculations based on the LVG formalism have been performed to derive molecular abundances from the innermost out to the outer layers. The excitation calculations include infrared pumping to excited vibrational states and inelastic collisions, for which up-to-date rate coefficients for rotational and, in some cases, ro-vibrational transitions are used. Results. We find that in the inner layers CS, SiO, and SiS have abundances relative to H 2 of 4 × 10 −6 , 1.8 × 10 −7 , and 3 × 10 −6 , respectively, and that CS and SiS have significant lower abundances in the outer envelope, which implies that they actively contribute to the formation of dust. Moreover, in the inner layers, the amount of sulfur and silicon in gas phase molecules is only 27% for S and 5.6% for Si, implying that these elements have already condensed onto grains, most likely in the form of MgS and SiC. Metal-bearing molecules lock up a relatively small fraction of metals, although our results indicate that NaCl, KCl, AlCl, AlF, and NaCN, despite their refractory character, are not significantly depleted in the cold outer layers. In these regions a few percent of the metals Na, K, and Al survive in the gas phase, either in atomic or molecular form, and are therefore available to participate in the gas phase chemistry in the outer envelope.

The high temperature contrast between the day and night sides of hot-Jupiter atmospheres may result in strong variations of the chemical composition with longitude if the atmosphere were at chemical equilibrium. On the other hand, the vigorous dynamics predicted in these atmospheres, with a strong equatorial jet, would tend to supress such longitudinal variations. To address this subject we have developed a pseudo two-dimensional model of a planetary atmosphere, which takes into account thermochemical kinetics, photochemistry, vertical mixing, and horizontal transport, the latter being modeled as a uniform zonal wind. We have applied the model to the atmospheres of the hot Jupiters HD 209458b and HD 189733b. The adopted eddy diffusion coefficients were calculated by following the behavior of passive tracers in three-dimensional general circulation models, which results in much lower eddy values than in previous estimates. We find that the distribution of molecules with altitude and longitude in the atmospheres of these two hot Jupiters is complex because of the interplay of the various physical and chemical processes at work. Much of the distribution of molecules is driven by the strong zonal wind and the limited extent of vertical transport, resulting in an important homogenization of the chemical composition with longitude. The homogenization is more marked in planets lacking a thermal inversion such as HD 189733b than in planets with a strong stratosphere such as HD 209458b. In general, molecular abundances are quenched horizontally to values typical of the hottest dayside regions, and thus the composition in the cooler nightside regions is highly contaminated by that of warmer dayside regions. As a consequence, the abundance of methane remains low, even below the predictions of previous one-dimensional models, which probably is in conflict with the high CH 4 content inferred from observations of the dayside of HD 209458b. Another consequence of the important longitudinal homogenization of the abundances is that the variability of the chemical composition has little effect on the way the emission spectrum is modified with phase and on the changes in the transmission spectrum from the transit ingress to the egress. These variations in the spectra are mainly due to changes in the temperature, rather than in the composition, between the different sides of the planet.

Chemical models have been developed over the years by astrophysicists to study the pro- cesses at play in the various environments of the interstellar medium (ISM) that define the chemical composition of the gas and the dust. These qualitative aspects of the model predictions have been improved from a chemical point of view thanks to many recent developments of the experimental technics and theoretical methods that aim at studying the individual reactions in conditions as close to the ISM conditions as possible and characterize the rate constants of their efficiency. These models have also been more and more associated with dynamical evolution of the ISM physical conditions (for star forming regions for instance) since the chemical composition is far from steady-state in such regions. In this paper, we try to assess the state of the art concerning the chemical modeling of dark clouds, the initial step for the formation of stars and disks.Comment: 61 pages, to be published in Chemical Reviews. This version of the paper may be slightly different from the published one since many modifications have done by the language edito

Aims. Following the recent detection of C 6 H − in the laboratory and in space we have succeeded in studying the microwave spectrum of C 4 H − . We report here the first detection in space of this negative ion. Methods. We have observed in the envelope of the carbon star IRC +10216 five lines corresponding to the J = 9−8, 11−10, 12−11, 14−13 and 15−14 rotational transitions of C 4 H − . The C 4 H − lines have a cusped shape, denoting that this ion is formed in the outer part of the envelope, like its neutral counterpart C 4 H. Results. The abundance of C 4 H − in IRC+10216 is 1/6 of the abundance of C 6 H − and 1/4200 of that of C 4 H. Conclusions. The detection of C 4 H− , after that of C 6 H − , confirms the theoretical prediction that C-chain anions are abundant in interstellar clouds and yields a first measurement of the electron radiative attachment rates.

We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes-ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination-is reviewed. Emphasis is placed on those key reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalyzed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase.

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