We present the fifth release of the UMIST Database for Astrochemistry (UDfA). The new reaction network contains 6173 gas-phase reactions, involving 467 species, 47 of which are new to this release. We have updated rate coefficients across all reaction types. We have included 1171 new anion reactions and updated and reviewed all photorates. In addition to the usual reaction network, we also now include, for download, state-specific deuterated rate coefficients, deuterium exchange reactions and a list of surface binding energies for many neutral species. Where possible, we have referenced the original source of all new and existing data. We have tested the main reaction network using a dark cloud model and a carbon-rich circumstellar envelope model. We present and briefly discuss the results of these models.

Context. Protoplanetary disks are vital objects in star and planet formation, possessing all the material, gas and dust, which may form a planetary system orbiting the new star. Small, simple molecules have traditionally been detected in protoplanetary disks; however, in the ALMA era, we expect the molecular inventory of protoplanetary disks to significantly increase. Aims. We investigate the synthesis of complex organic molecules (COMs) in protoplanetary disks to put constraints on the achievable chemical complexity and to predict species and transitions which may be observable with ALMA. Methods. We have coupled a 2D steady-state physical model of a protoplanetary disk around a typical T Tauri star with a large gas-grain chemical network including COMs. We compare the resulting column densities with those derived from observations and perform ray-tracing calculations to predict line spectra. We compare the synthesised line intensities with current observations and determine those COMs which may be observable in nearby objects. We also compare the predicted grain-surface abundances with those derived from cometary comae observations. Results. We find COMs are efficiently formed in the disk midplane via grain-surface chemical reactions, reaching peak grain-surface fractional abundances ∼10 −6 -10 −4 that of the H nuclei number density. COMs formed on grain surfaces are returned to the gas phase via non-thermal desorption; however, gas-phase species reach lower fractional abundances than their grain-surface equivalents, ∼10 −12 -10 −7 . Including the irradiation of grain mantle material helps build further complexity in the ice through the replenishment of grain-surface radicals which take part in further grain-surface reactions. There is reasonable agreement with several line transitions of H 2 CO observed towards T Tauri star-disk systems. There is poor agreement with HC 3 N lines observed towards LkCa 15 and GO Tau and we discuss possible explanations for these discrepancies. The synthesised line intensities for CH 3 OH are consistent with upper limits determined towards all sources. Our models suggest CH 3 OH should be readily observable in nearby protoplanetary disks with ALMA; however, detection of more complex species may prove challenging, even with ALMA "Full Science" capabilities. Our grain-surface abundances are consistent with those derived from cometary comae observations providing additional evidence for the hypothesis that comets (and other planetesimals) formed via the coagulation of icy grains in the Sun's natal disk.

Context. The atmospheres of extrasolar planets are thought to be built largely through accretion of pebbles and planetesimals. Such pebbles are also the building blocks of comets. The chemical composition of their volatiles are usually taken to be inherited from the ices in the collapsing cloud. However, chemistry in the protoplanetary disk midplane can modify the composition of ices and gases. Aims. To investigate if and how chemical evolution affects the abundances and distributions of key volatile species in the midplane of a protoplanetary disk in the 0.2-30 AU range. Methods. A disk model used in planet population synthesis models is adopted, providing temperature, density and ionisation rate at different radial distances in the disk midplane. A full chemical network including gas-phase, gas-grain interactions and grain-surface chemistry is used to evolve chemistry in time, for 1 Myr. Both molecular (inheritance from the parent cloud) and atomic (chemical reset) initial conditions are investigated. Results. Great diversity is observed in the relative abundance ratios of the main considered species: H 2 O, CO, CO 2 , CH 4 , O 2 , NH 3 and N 2 . The choice of ionisation level, the choice of initial abundances, as well as the extent of chemical reaction types included are all factors that affect the chemical evolution. The only exception is the inheritance scenario with a low ionisation level, which results in negligible changes compared with the initial abundances, regardless of whether grain-surface chemistry is included. The grain temperature plays an important role, especially in the critical 20-28 K region where atomic H no longer sticks long enough to the surface to react, but atomic O does. Above 28 K, efficient grain-surface production of CO 2 ice is seen, as well as O 2 gas and ice under certain conditions, at the expense of H 2 O and CO. H 2 O ice is produced on grain surfaces only below 28 K. For high ionisation levels at intermediate disk radii, CH 4 gas is destroyed and converted into CO and CO 2 (in contrast with previous models), and similarly NH 3 gas is converted into N 2 . At large radii around 30 AU, CH 4 ice is enhanced leading to a low gaseous CO abundance. As a result, the overall C/O ratios for gas and ice change significantly with radius and with model assumptions. For high ionisation levels, chemical processing becomes significant after a few times 10 5 yrs. Conclusions. Chemistry in the disk midplane needs to be considered in the determination of the volatile composition of planetesimals. In the inner <30 AU disk, interstellar ice abundances are preserved only if the ionisation level is low, or if these species are included in larger bodies within 10 5 yrs.

Context. Near-to mid-infrared observations of molecular emission from protoplanetary disks show that the inner regions are rich in small organic volatiles (e.g., C 2 H 2 and HCN). Trends in the data suggest that disks around cooler stars (T eff ≈ 3000 K) are potentially (i) more carbon-rich; and (ii) more molecule-rich than their hotter counterparts (T eff > ∼ 4000 K). Aims. We explore the chemical composition of the planet-forming region (<10 AU) of protoplanetary disks around stars over a range of spectral types (from M dwarf to Herbig Ae) and compare with the observed trends. Methods. Self-consistent models of the physical structure of a protoplanetary disk around stars of different spectral types are coupled with a comprehensive gas-grain chemical network to map the molecular abundances in the planet-forming zone. The effects of (i) N 2 self shielding; (ii) X-ray-induced chemistry; and (iii) initial abundances, are investigated. The chemical composition in the "observable" atmosphere is compared with that in the disk midplane where the bulk of the planet-building reservoir resides. Results. M dwarf disk atmospheres are relatively more molecule rich than those for T Tauri or Herbig Ae disks. The weak far-UV flux helps retain this complexity which is enhanced by X-ray-induced ion-molecule chemistry. N 2 self shielding has only a small effect in the disk molecular layer and does not explain the higher C 2 H 2 /HCN ratios observed towards cooler stars. The models underproduce the OH/H 2 O column density ratios constrained in Herbig Ae disks, despite reproducing (within an order of magnitude) the absolute value for OH: the inclusion of self shielding for H 2 O photodissociation only increases this discrepancy. One possible explanation is the adopted disk structure. Alternatively, the "hot" H 2 O (T > ∼ 300 K) chemistry may be more complex than assumed. The results for the atmosphere are independent of the assumed initial abundances; however, the composition of the disk midplane is sensitive to the initial main elemental reservoirs. The models show that the gas in the inner disk is generally more carbon rich than the midplane ices. This effect is most significant for disks around cooler stars. Furthermore, the atmospheric C/O ratio appears larger than it actually is when calculated using observable tracers only. This is because gas-phase O 2 is predicted to be a significant reservoir of atmospheric oxygen.Conclusions. The models suggest that the gas in the inner regions of disks around cooler stars is more carbon rich; however, calculations of the molecular emission are necessary to definitively confirm whether the chemical trends reproduce the observed trends.

The composition of the neutral gas comas of most comets is dominated by H2O, CO and CO2, typically comprising as much as 95 per cent of the total gas density. In addition, cometary comas have been found to contain a rich array of other molecules, including sulfuric compounds and complex hydrocarbons. Molecular oxygen (O2), however, despite its detection on other icy bodies such as the moons of Jupiter and Saturn, has remained undetected in cometary comas. Here we report in situ measurement of O2 in the coma of comet 67P/Churyumov-Gerasimenko, with local abundances ranging from one per cent to ten per cent relative to H2O and with a mean value of 3.80 ± 0.85 per cent. Our observations indicate that the O2/H2O ratio is isotropic in the coma and does not change systematically with heliocentric distance. This suggests that primordial O2 was incorporated into the nucleus during the comet's formation, which is unexpected given the low upper limits from remote sensing observations. Current Solar System formation models do not predict conditions that would allow this to occur.

The protoplanetary system HD 169142 is one of the few cases where a potential candidate protoplanet has recently been detected by direct imaging in the near-infrared. To study the interaction between the protoplanet and the disk itself, observations of the gas and dust surface density structure are needed. This paper reports new ALMA observations of the dust continuum at 1.3 mm, 12 CO, 13 CO, and C 18 O J = 2−1 emission from the system HD 169142 (which is observed almost face-on) at an angular resolution of ∼0 . 3 × 0 . 2 (∼35 × 20 au). The dust continuum emission reveals a double-ring structure with an inner ring between 0 . 17−0 . 28 (∼20−35 au) and an outer ring between 0 . 48−0 . 64 (∼56−83 au). The size and position of the inner ring is in good agreement with previous polarimetric observations in the near-infrared and is consistent with dust trapping by a massive planet. No dust emission is detected inside the inner dust cavity (R 20 au) or within the dust gap (∼35−56 au) down to the noise level. In contrast, the channel maps of the J = 2−1 line of the three CO isotopologs reveal gas inside the dust cavity and dust gap. The gaseous disk is also much larger than the compact dust emission; it extends to ∼1 . 5 (∼180 au) in radius. This difference and the sharp drop of the continuum emission at large radii point to radial drift of large dust grains (>µm size). Using the thermo-chemical disk code dali, we modeled the continuum and the CO isotopolog emission to quantitatively measure the gas and dust surface densities. The resulting gas surface density is reduced by a factor of ∼30−40 inward of the dust gap. The gas and dust distribution indicate that two giant planets shape the disk structure through dynamical clearing (dust cavity and gap) and dust trapping (double-ring dust distribution).

Context. Exoplanet atmospheres are thought be built up from accretion of gas as well as pebbles and planetesimals in the midplanes of planet-forming disks. The chemical composition of this material is usually assumed to be unchanged during the disk lifetime. However, chemistry can alter the relative abundances of molecules in this planet-building material. Aims. To assess the impact of disk chemistry during the era of planet formation. This is done by investigating the chemical changes to volatile gases and ices in a protoplanetary disk midplane out to 30 AU for up to 7 Myr, considering a variety of different conditions, including a physical midplane structure that is evolving in time, and also considering two disks with different masses.Methods. An extensive kinetic chemistry gas-grain reaction network is utilised to evolve the abundances of chemical species over time. Two disk midplane ionisation levels (low and high) are explored, as well as two different makeups of the initial abundances ("inheritance" or "reset"). Results. Given a high level of ionisation, chemical evolution in protoplanetary disk midplanes becomes significant after a few times 10 5 yrs, and is still ongoing by 7 Myr between the H 2 O and the O 2 icelines. Inside the H 2 O iceline, and in the outer, colder regions of the disk midplane outside the O 2 iceline, the relative abundances of the species reach (close to) steady state by 7 Myr. Importantly, the changes in the abundances of the major elemental carbon and oxygen-bearing molecules imply that the traditional "stepfunction" for the C/O ratios in gas and ice in the disk midplane (as defined by sharp changes at icelines of H 2 O, CO 2 and CO) evolves over time, and cannot be assumed fixed, with the C/O ratio in the gas even becoming smaller than the C/O ratio in the ice. In addition, at lower temperatures (< 29 K), gaseous CO colliding with the grains gets converted into CO 2 and other more complex ices, lowering the CO gas abundance between the O 2 and CO thermal icelines. This effect can mimic a CO iceline at a higher temperature than suggested by its binding energy. Conclusions. Chemistry in the disk midplane is ionisation-driven, and evolves over time. This affects which molecules go into forming planets and their atmospheres. In order to reliably predict the atmospheric compositions of forming planets, as well as to relate observed atmospheric C/O ratios of exoplanets to where and how the atmospheres have formed in a disk midplane, chemical evolution needs to be considered and implemented into planet formation models.

The cross-disciplinary field of astrochemistry exists to understand the formation, destruction, and survival of molecules in astrophysical environments. Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. A broad consensus has been reached in the astrochemistry community on how to suitably treat gas-phase processes in models, and also on how to present the necessary reaction data in databases; however, no such consensus has yet been reached for grain-surface processes. A team of ∼25 experts covering observational, laboratory and theoretical (astro)chemistry met in summer of 2014 at the Lorentz Center in Leiden with the aim to provide solutions for this problem and to review the current state-of-the-art of grain surface models, both in terms of technical implementation into models as well as the most up-to-date information available from experiments and chemical computations. This review builds on the results of this workshop and gives an outlook for future directions.