Context. Molecular hydrogen (H2) is the main constituent of the gas in the planet-forming disks that surround many pre-main-sequence stars. H2 can be incorporated in the atmosphere of the nascent giant planets in disks. Deuterium hydride (HD) has been detected in a few disks and can be considered the most reliable tracer of H2, provided that its abundance throughout the disks with respect to H2 is well understood. Aims. We wish to form H2 and HD efficiently for the varied conditions encountered in protoplanetary disks: the densities vary from 104 to 1016 cm-3; the dust temperatures range from 5 to 1500 K, the gas temperatures go from 5 to a few 1000 Kelvin, and the ultraviolet radiation field can be 107 stronger than the standard interstellar field. Methods. We implemented a comprehensive model of H2 and HD formation on cold and warm grain surfaces and via hydrogenated polycyclic aromatic hydrocarbons in the physico-chemical code PROtoplanetary DIsk MOdel. The H2 and HD formation on dust grains can proceed via the Langmuir-Hinshelwood and Eley-Ridel mechanisms for physisorbed or chemisorbed H (D) atoms. H2 and HD also form by H (D) abstraction from hydrogenated neutral and ionised PAHs and via gas phase reactions. Results. H2 and HD are formed efficiently on dust grain surfaces from 10 to ∼700 K. All the deuterium is converted into HD in UV shielded regions as soon as H2 is formed by gas-phase D abstraction reactions. The detailed model compares well with standard analytical prescriptions for H2 (HD) formation. At low temperature, H2 is formed from the encounter of two physisorbed atoms. HD molecules form on the grain surfaces and in the gas-phase. At temperatures greater than 20 K, the encounter between a weakly bound H-(or D-) atom or a gas-phase H (D) atom and a chemisorbed atom is the most efficient H2 formation route. H2 formation through hydrogenated PAHs alone is efficient above 80 K. However, the contribution of hydrogenated PAHs to the overall H2 and HD formation is relatively low if chemisorption on silicate is taken into account and if a small hydrogen abstraction cross-section is used. The H2 and HD warm grain surface network is a first step in the construction of a network of high-temperature surface reactions. @en

Context. The origin of the reservoirs of water on Earth is debated. The Earth's crust may contain at least three times more water than the oceans. This crust water is found in the form of phyllosilicates, whose origin probably differs from that of the oceans. Aims. We test the possibility to form phyllosilicates in protoplanetary disks, which can be the building blocks of terrestrial planets. Methods. We developed an exploratory rate-based warm surface chemistry model where water from the gas-phase can chemisorb on dust grain surfaces and subsequently diffuse into the silicate cores. We applied the phyllosilicate formation to a zero-dimensional chemical model and to a 2D protoplanetary disk model (PRODIMO). The disk model includes in addition to the cold and warm surface chemistry continuum and line radiative transfer, photoprocesses (photodissociation, photoionisation, and photodesorption), gas-phase cold and warm chemistry including three-body reactions, and detailed thermal balance. Results. Despite the high energy barrier for water chemisorption on silicate grain surfaces and for diffusion into the core, the chemisorption sites at the surfaces can be occupied by a hydroxyl bond (-OH) at all gas and dust temperatures from 80 to 700 K for a gas density of 2 × 104 cm-3. The chemisorption sites in the silicate cores are occupied at temperatures between 250 and 700 K. At higher temperatures thermal desorption of chemisorbed water occurs. The occupation efficiency is only limited by the maximum water uptake of the silicate. The timescales for complete hydration are at most 105 yr for 1 mm radius grains at a gas density of 108 cm-3. Conclusions. Phyllosilicates can be formed on dust grains at the dust coagulation stage in protoplanetary disks within 1 Myr. It is however not clear whether the amount of phyllosilicate formed by warm surface chemistry is sufficient compared to that found in Solar System objects.@en

Context. Interstellar dust particles, which represent 1% of the total mass, are recognized to be very powerful interstellar catalysts in star-forming regions. The presence of dust can have a strong impact on the chemical composition of molecular clouds. While observations show that many species that formed onto dust grains populate the gas phase, the process that transforms solid state into gas phase remains unclear. Aims. The aim of this paper is to consider the chemical desorption process, i.e. the process that releases solid species into the gas phase, in astrochemical models. These models allow determining the chemical composition of star-forming environments with an accurate treatment of the solid-phase chemistry. Methods. In paper I we derived a formula based on experimental studies with which we quantified the efficiencies of the chemical desorption process. Here we extend these results to astrophysical conditions. Results. The simulations of astrophysical environments show that the abundances of gas-phase methanol and H2O2 increase by four orders of magnitude, whereas gas-phase H2CO and HO2 increase by one order of magnitude when the chemical desorption process is taken into account. The composition of the ices strongly varies when the chemical desorption is considered or neglected. Conclusions. We show that the chemical desorption process, which directly transforms solid species into gas-phase species, is very efficient for many reactions. Applied to astrophysical environments such as ρ Oph A, we show that the chemical desorption efficiencies derived in this study reproduce the abundances of observed gas-phase methanol, HO2, and H2O2, and that the presence of these molecules in the gas shows the last signs of the evolution of a cloud before the frost.@en

Context. The presence of dust in the interstellar medium has profound consequences on the chemical composition of regions where stars are forming. Recent observations show that many species formed onto dust are populating the gas phase, especially in cold environments where UV- and cosmic-ray-induced photons do not account for such processes. Aims. The aim of this paper is to understand and quantify the process that releases solid species into the gas phase, the so-called chemical desorption process, so that an explicit formula can be derived that can be included in astrochemical models. Methods. We present a collection of experimental results of more than ten reactive systems. For each reaction, different substrates such as oxidized graphite and compact amorphous water ice were used. We derived a formula for reproducing the efficiencies of the chemical desorption process that considers the equipartition of the energy of newly formed products, followed by classical bounce on the surface. In part II of this study we extend these results to astrophysical conditions. Results. The equipartition of energy correctly describes the chemical desorption process on bare surfaces. On icy surfaces, the chemical desorption process is much less efficient, and a better description of the interaction with the surface is still needed. Conclusions. We show that the mechanism that directly transforms solid species into gas phase species is efficient for many reactions.@en

When studying chemistry of photodissociation regions (PDRs), time dependence becomes important as visual extinction increases, since certain chemical time-scales are comparable to the cloud lifetime. Dust temperature is also a key factor, since it significantly influences gas temperature and mobility on dust grains, determining the chemistry occurring on grain surfaces. We present a study of the dust temperature impact and time effects on the chemistry of different PDRs, using an updated version of theMeijerink PDR code and combining it with the time-dependent code Nahoon. We find the largest temperature effects in the inner regions of highG0 PDRs,where high dust temperatures favour the formation of simple oxygen-bearing molecules (especially that of O2), while the formation of complex organic molecules is much more efficient at low dust temperatures. We also find that time-dependent effects strongly depend on the PDR type, since long time-scales promote the destruction of oxygen-bearing molecules in the inner parts of low G0 PDRs, while favouring their formation and that of carbon-bearing molecules in high G0 PDRs. From the chemical evolution, we also conclude that, in dense PDRs, CO2 is a late-forming ice compared to water ice, and confirm a layered ice structure on dust grains, with H2O in lower layers than CO2. Regarding steady state, the PDR edge reaches chemical equilibrium at early times (≲105 yr). This time is even shorter (<104 yr) for high G0 PDRs. By contrast, inner regions reach equilibrium much later, especially low G0 PDRs, where steady state is reached at ∼106-107 yr.@en

The temperature of interstellar dust particles is of great importance to astronomers. It plays a crucial role in the thermodynamics of interstellar clouds, because of the gas-dust collisional coupling. It is also a key parameter in astrochemical studies that governs the rate at which molecules form on dust. In 3D (magneto)hydrodynamic simulations often a simple expression for the dust temperature is adopted, because of computational constraints, while astrochemical modelers tend to keep the dust temperature constant over a large range of parameter space. Our aim is to provide an easy-to-use parametric expression for the dust temperature as a function of visual extinction (AV) and to shed light on the critical dependencies of the dust temperature on the grain composition. We obtain an expression for the dust temperature by semi-analytically solving the dust thermal balance for different types of grains and compare to a collection of recent observational measurements. We also explore the effect of ices on the dust temperature. Our results show that a mixed carbonaceous-silicate type dust with a high carbon volume fraction matches the observations best. We find that ice formation allows the dust to be warmer by up to 15% at high optical depths (AV> 20 mag) in the interstellar medium. Our parametric expression for the dust temperature is presented as Td = [11 + 5.7 × tanh(0.61 - log 10(AV)]χuv 1/5.9, where χuv is in units of the Draine (1978, ApJS, 36, 595) UV field.@en

In the earliest phases of star-forming clouds, stable molecular species, such as CO, are important coolants in the gas phase. Depletion of these molecules on dust surfaces affects the thermal balance of molecular clouds and with that their whole evolution. For the first time, we study the effect of grain surface chemistry (GSC) on star formation and its impact on the initial mass function (IMF). We follow a contracting translucent cloud in which we treat the gas-grain chemical interplay in detail, including the process of freeze-out. We perform 3D hydrodynamical simulations under three different conditions, a pure gas-phase model, a freeze-out model, and a complete chemistry model. The models display different thermal evolution during cloud collapse as also indicated in Hocuk, Cazaux & Spaans, but to a lesser degree because of a different dust temperature treatment, which is more accurate for cloud cores. The equation of state (EOS) of the gas becomes softer with CO freeze-out and the results show that at the onset of star formation, the cloud retains its evolution history such that the number of formed stars differ (by 7 per cent) between the three models. While the stellar mass distribution results in a different IMF when we consider pure freeze-out, with the complete treatment of the GSC, the divergence from a pure gas-phase model is minimal. We find that the impact of freeze-out is balanced by the non-thermal processes; chemical and photodesorption. We also find an average filament width of 0.12 pc (±0.03 pc), and speculate that this may be a result from the changes in the EOS caused by the gas-dust thermal coupling. We conclude that GSC plays a big role in the chemical composition of molecular clouds and that surface processes are needed to accurately interpret observations, however, that GSC does not have a significant impact as far as star formation and the IMF is concerned.@en

Star formation in the centers of galaxies is thought to yield massive stars with a possibly top-heavy stellar mass distribution. It is likely that magnetic fields play a crucial role in the distribution of stellar masses inside star-forming molecular clouds. In this context, we explore the effects of magnetic fields, with a typical field strength of 38 μG, such as in RCW 38, and a field strength of 135 μG, similar to NGC 2024 and the infrared dark cloud G28.34+0.06, on the initial mass function (IMF) near (=10 pc) a 107 solar mass black hole. Using these conditions, we perform a series of numerical simulations with the hydrodynamical code FLASH to elucidate the impact of magnetic fields on the IMF and the star-formation efficiency (SFE) emerging from an 800 solar mass cloud. We find that the collapse of a gravitationally unstable molecular cloud is slowed down with increasing magnetic field strength and that stars form along the field lines. The total number of stars formed during the simulations increases by a factor of 1.5-2 with magnetic fields. The main component of the IMF has a lognormal shape, with its peak shifted to sub-solar (=0.3 M·) masses in the presence of magnetic fields, due to a decrease in the accretion rates from the gas reservoir. In addition, we see a top-heavy, nearly flat IMF above ∼2 solar masses, from regions that were supported by magnetic pressure until high masses are reached. We also consider the effects of X-ray irradiation if the central black hole is active. X-ray feedback inhibits the formation of sub-solar masses and decreases the SFEs even further. Thus, the second contribution is no longer visible. We conclude that magnetic fields potentially change the SFE and the IMF both in active and inactive galaxies, and need to be taken into account in such calculations. The presence of a flat component of the IMF would be a particularly relevant signature for the importance of magnetic fields, as it is usually not found in hydrodynamical simulations.@en

During the evolution of diffuse clouds to molecular clouds, gas-phase molecules freeze out on surfaces of small dust particles to form ices. On dust surfaces, water is the main constituent of the icy mantle in which a complex chemistry is taking place. We aim to study the formation pathways and the composition of the ices throughout the evolution of diffuse clouds. For this purpose, we used time-dependent rate equations to calculate the molecular abundances in the gas phase and on solid surfaces (onto dust grains). We fully considered the gas-dust interplay by including the details of freeze-out, chemical and thermal desorption, and the most important photo-processes on grain surfaces. The difference in binding energies of chemical species on bare and icy surfaces was also incorporated into our equations. Using the numerical code flash, we performed a hydrodynamical simulation of a gravitationally bound diffuse cloud and followed its contraction. We find that while the dust grains are still bare, water formation is enhanced by grain surface chemistry that is subsequently released into the gas phase, enriching the molecular medium. The CO molecules, on the other hand, tend to gradually freeze out on bare grains. This causes CO to be well mixed and strongly present within the first ice layer. Once one monolayer of water ice has formed, the binding energy of the grain surface changes significantly, and an immediate and strong depletion of gas-phase water and CO molecules occurs. While hydrogenation converts solid CO into formaldehyde (H2CO) and methanol (CH3OH), water ice becomes the main constituent of the icy grains. Inside molecular clumps formaldehyde is more abundant than water and methanol in the gas phase, owing its presence in part to chemical desorption.@en

Context. Spectroscopic studies of ices in nearby star-forming regions indicate that ice mantles form on dust grains in two distinct steps, starting with polar ice formation (H2O rich) and switching to apolar ice (CO rich). Aims. We test how well the picture applies to more diffuse and quiescent clouds where the formation of the first layers of ice mantles can be witnessed. Methods. Medium-resolution near-infrared spectra are obtained toward background field stars behind the Pipe Nebula. Results. The water ice absorption is positively detected at 3.0 µm in seven lines of sight out of 21 sources for which observed spectra are successfully reduced. The peak optical depth of the water ice is significantly lower than those in Taurus with the same AV . The source with the highest water-ice optical depth shows CO ice absorption at 4.7 µm as well. The fractional abundance of CO ice with respect to water ice is 16+7 −6 %, and about half as much as the values typically seen in low-mass star-forming regions. Conclusions. A small fractional abundance of CO ice is consistent with some of the existing simulations. Observations of CO2 ice in the early diffuse phase of a cloud play a decisive role in understanding the switching mechanism between polar and apolar ice formation.@en

Atoms and molecules, and in particular CO, are important coolants during the evolution of interstellar star-forming gas clouds. The presence of dust grains, which allow many chemical reactions to occur on their surfaces, strongly impacts the chemical composition of a cloud. At low temperatures, dust grains can lock up species from the gas phase which freeze out and form ices. In this sense, dust can deplete important coolants. Our aim is to understand the effects of freeze-out on the thermal balance and the evolution of a gravitationally bound molecular cloud. For this purpose, we perform 3D hydrodynamical simulations with the adaptive mesh code FLASH. We simulate a gravitationally unstable cloud under two different conditions, with and without grain surface chemistry. We let the cloud evolve until one free-fall time is reached and track the thermal evolution and the abundances of species during this time. We see that at a number density of 104 cm-3 most of the CO molecules are frozen on dust grains in the run with grain surface chemistry, thereby depriving the most important coolant. As a consequence, we find that the temperature of the gas rises up to ̃25 K. The temperature drops once again due to gas-grain collisional cooling when the density reaches a few × 104 cm-3.We conclude that grain surface chemistry not only affects the chemical abundances in the gas phase, but also leaves a distinct imprint in the thermal evolution that impacts the fragmentation of a star-forming cloud. As a final step, we present the equation of state of a collapsing molecular cloud that has grain surface chemistry included.@en