The evolution of star-forming regions and their thermal balance are strongly influenced by their chemical composition, which, in turn, is determined by the physicochemical processes that govern the transition between the gas phase and the solid state, specifically icy dust grains (e.g., particle adsorption and desorption). Gas-grain and grain-gas transitions as well as formation and sublimation of interstellar ices are thus essential elements of understanding astrophysical observations of cold environments (e.g., prestellar cores) where unexpected amounts of a large variety of chemical species have been observed in the gas phase. Adsorbed atoms and molecules also undergo chemical reactions that are not efficient in the gas phase. Therefore, the parametrization of the physical properties of atoms and molecules interacting with dust grain particles is clearly a key aspect to interpret astronomical observations and to build realistic and predictive astrochemical models. In this consensus evaluation, we focus on parameters controlling the thermal desorption of ices and how these determine pathways toward molecular complexity and define the location of snowlines, which ultimately influence the planet formation process. We review different crucial aspects of desorption parameters both from a theoretical and experimental points of view. We critically assess the desorption parameters (the binding energies, Eb, and the pre-exponential factor, ν) commonly used in the astrochemical community for astrophysically relevant species and provide tables with recommended values. The aim of these tables is to provide a coherent set of critically assessed desorption parameters for common use in future work. In addition, we show that a nontrivial determination of the pre-exponential factor ν using transition state theory can affect the binding energy value. The primary focus is on pure ices, but we also discuss the desorption behavior of mixed, that is, astronomically more realistic, ices. This allows discussion of segregation effects. Finally, we conclude this work by discussing the limitations of theoretical and experimental approaches currently used to determine the desorption properties with suggestions for future improvements.@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

At the low temperatures of interstellar dust grains, it is well established that surface chemistry proceeds via diffusive mechanisms of H atoms weakly bound (physisorbed) to the surface. Until recently, however, it was unknown whether atoms heavier than hydrogen could diffuse rapidly enough on interstellar grains to react with other accreted species. In addition, models still require simple reduction as well as oxidation reactions to occur on grains to explain the abundances of various molecules. In this paper we investigate O-atom diffusion and reactivity on a variety of astrophysically relevant surfaces (water ice of three different morphologies, silicate, and graphite) in the 6.5-25 K temperature range. Experimental values were used to derive a diffusion law that emphasizes that O atoms diffuse by quantum mechanical tunnelling at temperatures as low as 6.5 K. The rates of diffusion on each surface, based on modelling results, were calculated and an empirical law is given as a function of the surface temperature. The relative diffusion rates are kH2Oice > ksil > kgraph ≫ kexpected. The implications of efficient O-atom diffusion over astrophysically relevant time-scales are discussed. Our findings show that O atoms can scan any available reaction partners (e.g., either another H atom, if available, or a surface radical like O or OH) at a faster rate than that of accretion. Also, as dense clouds mature, H2 becomes far more abundant than H and the O:H ratio grows, and the reactivity of O atoms on grains is such that O becomes one of the dominant reactive partners together with H. This journal is@en

At the low temperatures of interstellar dust grains, it is well established that surface chemistry proceeds via diffusive mechanisms of H atoms weakly bound (physisorbed) to the surface. Until recently, however, it was unknown whether atoms heavier than hydrogen could diffuse rapidly enough on interstellar grains to react with other accreted species. In addition, models still require simple reduction as well as oxidation reactions to occur on grains to explain the abundances of various molecules. In this paper we investigate O-atom diffusion and reactivity on a variety of astrophysically relevant surfaces (water ice of three different morphologies, silicate, and graphite) in the 6.5-25 K temperature range. Experimental values were used to derive a diffusion law that emphasizes that O atoms diffuse by quantum mechanical tunnelling at temperatures as low as 6.5 K. The rates of diffusion on each surface, based on modelling results, were calculated and an empirical law is given as a function of the surface temperature. The relative diffusion rates are kH2Oice > ksil > kgraph ≫ kexpected. The implications of efficient O-atom diffusion over astrophysically relevant time-scales are discussed. Our findings show that O atoms can scan any available reaction partners (e.g., either another H atom, if available, or a surface radical like O or OH) at a faster rate than that of accretion. Also, as dense clouds mature, H2 becomes far more abundant than H and the O:H ratio grows, and the reactivity of O atoms on grains is such that O becomes one of the dominant reactive partners together with H. This journal is@en

Any evolving system can change state via thermal mechanisms (hopping a barrier) or via quantum tunneling. Most of the time, efficient classical mechanisms dominate at high temperatures. This is why an increase of the temperature can initiate the chemistry. We present here an experimental investigation of O-atom diffusion and reactivity on water ice. We explore the 6-25 K temperature range at submonolayer surface coverages. We derive the diffusion temperature law and observe the transition from quantum to classical diffusion. Despite the high mass of O, quantum tunneling is efficient even at 6 K. As a consequence, the solid-state astrochemistry of cold regions should be reconsidered and should include the possibility of forming larger organic molecules than previously expected.@en

Any evolving system can change state via thermal mechanisms (hopping a barrier) or via quantum tunneling. Most of the time, efficient classical mechanisms dominate at high temperatures. This is why an increase of the temperature can initiate the chemistry. We present here an experimental investigation of O-atom diffusion and reactivity on water ice. We explore the 6-25 K temperature range at submonolayer surface coverages. We derive the diffusion temperature law and observe the transition from quantum to classical diffusion. Despite the high mass of O, quantum tunneling is efficient even at 6 K. As a consequence, the solid-state astrochemistry of cold regions should be reconsidered and should include the possibility of forming larger organic molecules than previously expected.@en

Any evolving system can change state via thermal mechanisms (hopping a barrier) or via quantum tunneling. Most of the time, efficient classical mechanisms dominate at high temperatures. This is why an increase of the temperature can initiate the chemistry. We present here an experimental investigation of O-atom diffusion and reactivity on water ice. We explore the 6-25 K temperature range at submonolayer surface coverages. We derive the diffusion temperature law and observe the transition from quantum to classical diffusion. Despite the high mass of O, quantum tunneling is efficient even at 6 K. As a consequence, the solid-state astrochemistry of cold regions should be reconsidered and should include the possibility of forming larger organic molecules than previously expected.@en

In the environments where stars and planets form, about one percent of the mass is in the form of micro-meter sized particles known as dust. However small and insignificant these dust grains may seem, they are responsible for the production of the simplest (H 2) to the most complex (amino-acids) molecules observed in our Universe. Dust particles are recognized as powerful nano-factories that produce chemical species. However, the mechanism that converts species on dust to gas species remains elusive. Here we report experimental evidence that species forming on interstellar dust analogs can be directly released into the gas. This process, entitled chemical desorption (fig. 1), can dominate over the chemistry due to the gas phase by more than ten orders of magnitude. It also determines which species remain on the surface and are available to participate in the subsequent complex chemistry that forms the molecules necessary for the emergence of life.@en