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.

Aims. Molecular hydrogen is the most abundant molecule in the Universe. It is thought that a large portion of H₂ forms by association of hydrogen atoms to polycyclic aromatic hydrocarbons (PAHs). We model the influence of PAHs on total H₂ formation rates in photodissociation regions (PDRs) and assess the effect of these formation rates on the total cloud structure. Methods. We set up a chemical kinetic model at steady state in a PDR environment and included radiative transfer to calculate the chemistry at different depths in the PDR. This model includes known dust grain chemistry for the formation of H₂ and a H₂ formation mechanism on PAHs. Since H₂ formation on PAHs is impeded by thermal barriers, this pathway is only efficient at higher temperatures (T> 200 K). At these temperatures the conventional route of H₂ formation via H atoms physisorbed on dust grains is no longer feasible, so the PAH mechanism enlarges the region where H₂ formation is possible. Results. We find that PAHs have a significant influence on the structure of PDRs. The extinction at which the transition from atomic to molecular hydrogen occurs strongly depends on the presence of PAHs, especially for PDRs with a strong external radiation field. A sharp spatial transition between fully dehydrogenated PAHs on the outside of the cloud and normally hydrogenated PAHs on the inside is found. As a proof of concept, we use coronene to show that H₂ forms very efficiently on PAHs, and that this process can reproduce the high H₂ formation rates derived in several PDRs.

Molecular hydrogen is the most abundant molecule in the universe. A large fraction of H₂ forms by association of hydrogen atoms adsorbed on polycyclic aromatic hydrocarbons (PAHs), where formation rates depend crucially on the H sticking probability. We have experimentally studied PAH hydrogenation by exposing coronene cations, confined in a radio-frequency ion trap, to gas phase atomic hydrogen. A systematic increase of the number of H atoms adsorbed on the coronene with the time of exposure is observed. Odd coronene hydrogenation states dominate the mass spectrum up to 11 H atoms attached. This indicates the presence of a barrier preventing H attachment to these molecular systems. For the second and fourth hydrogenations, barrier heights of 72 ± 6 meV and 40 ± 10 meV, respectively, are found, which are in good agreement with theoretical predictions for the hydrogenation of neutral PAHs. Our experiments, however, prove that the barrier does not vanish for higher hydrogenation states. These results imply that PAH cations, as their neutral counterparts, exist in highly hydrogenated forms in the interstellar medium. Due to this catalytic activity, PAH cations and neutrals seem to contribute similarly to the formation of H₂.