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.@en

We have investigated the response of superhydrogenated gas-phase coronene cations upon soft x-ray absorption. Carbon (1s) transitions were resonantly excited at hν=285eV. The resulting core hole is then filled in an Auger decay process, with the excess energy being released in the form of an Auger electron. Predominantly highly excited dications are thus formed, which cool down by hydrogen emission. In superhydrogenated systems, the additional H atoms act as a buffer, quenching loss of native H atoms and molecular fragmentation. Dissociation and transition state energies for several H loss channels were computed by means of density functional theory. Using these energies as input into an Arrhenius-type cascade model, very good agreement with the experimental data is found. The results have important implications for the survival of polyaromatic hydrocarbons in the interstellar medium and reflect key aspects of graphene hydrogenation.@en