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.

We present a novel chemical database for gas-phase astrochemistry. Named the KInetic Database for Astrochemistry (KIDA), this database consists of gas-phase reactions with rate coefficients and uncertainties that will be vetted to the greatest extent possible. Submissions of measured and calculated rate coefficients are welcome, and will be studied by experts before inclusion into the database. Besides providing kinetic information for the interstellar medium, KIDA is planned to contain such data for planetary atmospheres and for circumstellar envelopes. Each year, a subset of the reactions in the database (kida.uva) will be provided as a network for the simulation of the chemistry of dense interstellar clouds with temperatures between 10 K and 300 K. We also provide a code, named Nahoon, to study the timedependent gas-phase chemistry of 0D and 1D interstellar sources.

We present an extended version of the 2-phase gas-grain code NAUTILUS to the 3phase modelling of gas and grain chemistry of cold cores. In this model, both the mantle and the surface are considered as chemically active. We also take into account the competition among reaction, diffusion and evaporation. The model predictions are confronted to ice observations in the envelope of low-mass and massive young stellar objects as well as toward background stars. Modelled gas-phase abundances are compared to species observed toward TMC-1 (CP) and L134N dark clouds. We find that our model successfully reproduces the observed ice species. It is found that the reaction-diffusion competition strongly enhances reactions with barriers and more specifically reactions with H 2 , which is abundant on grains. This finding highlights the importance to have a good approach to determine the abundance of H 2 on grains. Consequently, it is found that the major N-bearing species on grains go from NH 3 to N 2 and HCN when the reaction-diffusion competition is accounted. In the gasphase and before few 10 5 yrs, we find that the 3-phase model does not have a strong impact on the observed species compared to the 2-phase model. After this time, the computed abundances dramatically decrease due to the strong accretion on dust, which is not counterbalanced by the desorption less efficient than in the 2-phase model. This strongly constrains the chemical-age of cold cores to be of the order of few 10 5 yrs.

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.

Context. We describe and benchmark two sophisticated chemical models developed by the Heidelberg and Bordeaux astrochemistry groups. Aims. The main goal of this study is to elaborate on a few well-described tests for state-of-the-art astrochemical codes covering a range of physical conditions and chemical processes, in particular those aimed at constraining current and future interferometric observations of protoplanetary disks. Methods. We considered three physical models: a cold molecular cloud core, a hot core, and an outer region of a T Tauri disk. Our chemical network (for both models) is based on the original gas-phase osu_03_2008 ratefile and includes gas-grain interactions and a set of surface reactions for the H-, O-, C-, S-, and N-bearing molecules. The benchmarking was performed with the increasing complexity of the considered processes: (1) the pure gas-phase chemistry, (2) the gas-phase chemistry with accretion and desorption, and (3) the full gas-grain model with surface reactions. The chemical evolution is modeled within 10 9 years using atomic initial abundances with heavily depleted metals and hydrogen in its molecular form. Results. The time-dependent abundances calculated with the two chemical models are essentially the same for all considered physical cases and for all species, including the most complex polyatomic ions and organic molecules. This result, however, required a lot of effort to make all necessary details consistent through the model runs, e.g., definition of the gas particle density, density of grain surface sites, or the strength and shape of the UV radiation field. Conclusions. The reference models and the benchmark setup, along with the two chemical codes and resulting time-dependent abundances are made publicly available on the internet. This will facilitate and ease the development of other astrochemical models and provide nonspecialists with a detailed description of the model ingredients and requirements to analyze the cosmic chemistry as studied, e.g., by (sub-) millimeter observations of molecular lines.

We investigate the molecular evolution and D/H abundance ratios that develop as star formation proceeds from a dense-cloud core to a protostellar core, by solving a gas-grain reaction network applied to a 1-D radiative hydrodynamic model with infalling fluid parcels. Spatial distributions of gas and ice-mantle species are calculated at the first-core stage, and at times after the birth of a protostar. Gas-phase methanol and methane are more abundant than CO at radii r 100 AU in the first-core stage, but gradually decrease with time,

Planetary embryos embedded in gaseous protoplanetary disks undergo Type I orbital migration. Migration can be inward or outward depending on the local disk properties but, in general, only planets more massive than several M ⊕ can migrate outward. Here we propose that an embryo's migration history determines whether it becomes a hot super-Earth or the core of a giant planet. Systems of hot super-Earths (or mini-Neptunes) form when embryos migrate inward and pile up at the inner edge of the disk. Giant planet cores form when inward-migrating embryos become massive enough to switch direction and migrate outward. We present simulations of this process using a modified N-body code, starting from a swarm of planetary embryos. Systems of hot super-Earths form in resonant chains with the innermost planet at or interior to the disk inner edge. Resonant chains are disrupted by late dynamical instabilities triggered by the dispersal of the gaseous disk. Giant planet cores migrate outward toward zero-torque zones, which move inward and eventually disappear as the disk disperses. Giant planet cores migrate inward with these zones and are stranded at ∼1−5 AU. Our model reproduces several properties of the observed extra-solar planet populations. The frequency of giant planet cores increases strongly when the mass in solids is increased, consistent with the observed giant exoplanet -stellar metallicity correlation. The frequency of hot super-Earths is not a function of stellar metallicity, also in agreement with observations. Our simulations can reproduce the broad characteristics of the observed super-Earth population.

Recent observations have revealed the existence of Complex Organic Molecules (COMs) in cold dense cores and prestellar cores. The presence of these molecules in such cold conditions is not well understood and remains a matter of debate since the previously proposed "warmup" scenario cannot explain these observations. In this article, we study the effect of EleyRideal and complex induced reaction mechanisms of gas-phase carbon atoms with the main ice components of dust grains on the formation of COMs in cold and dense regions. Based on recent experiments we use a low value for the chemical desorption efficiency (which was previously invoked to explain the observed COM abundances). We show that our introduced mechanisms are efficient enough to produce a large amount of complex organic molecules in the gas-phase at temperatures as low as 10K.