Abstract: When exposed to a thermal beam of hydrogen atoms, gas-phase coronene cations C₂₄H₁₂⁺ can be sequentially hydrogenated. This process is accompanied by a gradual transition of the electronic structure from aromatic to aliphatic. The planar very stable coronene structure transforms into the significantly weaker corrugated structure, typical for aliphatic molecules. In this study, we have investigated the hydrogenation of 5 smaller polycyclic aromatic hydrocarbon cations using a combination of radiofrequency ion trapping with time-of-flight mass spectrometry. Anthracene (C₁₄H₁₀⁺), pyrene (C₁₆H₁₀⁺), triphenylene (C₁₈H₁₂⁺), tetracene (C₁₈H₁₂⁺) and 8-9-benzofluoranthene (C₂₀H₁₂⁺) only cover a small mass range, but differ in carbon/hydrogen ratio, number of outer-edge sites and overall structure. We have observed qualitatively similar initial hydrogenation patterns for all 5 molecular ions, with odd hydrogenation states being dominant. Strong quantitative differences in hydrogenation and in attachment-induced fragmentation were found. For the case of pyrene cations, we have also investigated exposure to atomic D. Clear lines of evidence for HD/D₂ abstraction reactions of Eley–Rideal type were found, as previously observed for coronene cations. Graphical abstract: [Figure not available: see fulltext.].

The solar magnetic field (SMF) has historically been considered as dipole in order to build models of the radially expanding corona, that is, the solar wind in the solar minimum. The simplified approach suggests the existence of only one quasi-stationary current sheet (QCS) of solar origin in the heliosphere, namely, the heliospheric current sheet (HCS). However, the SMF becomes more complicated over the solar cycle, comprising higher-order components. The overlapping of the dipole and multipole components of the SMF suggests a formation of more than one QCS in the corona, which may expand further to the heliosphere. We study the impact of the.,Qquadrupole and octupole harmonics of the SMF on the formation and spatial characteristics of QCSs, building a stationary axisymmetric MHD model of QCSs in the heliosphere. It is shown that if the dipole component dominates, a single QCS appears in the solar wind at low heliolatitudes as the classic HCS. In other.,Qcases, the number of QCSs varies from one to three, depending on the relative input of the quadrupole and octupole components. QCSs possess a conic form and may occur at a wide variety of heliolatitudes. The existence of QCSs opens wide opportunities for explanations of puzzling observations of cosmic rays and energetic particles in the heliosphere and, at the same time, raises a risk of misinterpretation of in situ crossings of QCSs because of mixing up the HCS and higherheliolatitude QCSs, which can be significantly disturbed in the dynamical solar wind.

We present experimental data on H₂ formation processes on gas-phase polycyclic aromatic hydrocarbon (PAH) cations. This process was studied by exposing coronene radical cations, confined in a radio-frequency ion trap, to gas-phase H atoms. Sequential attachment of up to 23 hydrogen atoms has been observed. Exposure to atomic D instead of H allows one to distinguish attachment from competing abstraction reactions, as the latter now leave a unique fingerprint in the measured mass spectra. Modelling of the experimental results using realistic cross-sections and barriers for attachment and abstraction yield a 1:2 ratio of abstraction to attachment cross-sections. The strong contribution of abstraction indicates that H2 formation on interstellar PAH cations is an order of magnitude more relevant than previously thought.

Sequential hydrogenation of polycyclic aromatic hydrocarbon (PAH) cations drives a gradual transition from a planar to a puckered geometry and from an aromatic to an aliphatic electronic structure. The resulting H-induced weakening of the molecular structure together with the exothermic nature of the consecutive H-attachment processes can lead to substantial molecular fragmentation. We have studied H attachment to gas-phase coronene cations in a radiofrequency ion trap using tandem mass spectrometry. With increasing hydrogenation, C₂H_i loss and multifragmentation are identified as main de-excitation channels. To understand the dependence of both channels on H-exposure time, we have simulated the molecular stability and fragmentation channels of hydrogenated PAHs using a molecular dynamics approach employing potential energies determined by a density functional based tight binding method. As the coronene fragmentation patterns depend on the balance between energy deposition by H-attachment and the extent of cooling in between subsequent attachment processes, we investigate several scenarios for the energy distribution of hydrogenated PAHs. Good agreement between experiment and simulation is reached, when realistic energy distributions are considered.

The understanding of hydrogen attachment to carbonaceous surfaces is essential to a wide variety of research fields and technologies such as hydrogen storage for transportation, precise localization of hydrogen in electronic devices and the formation of cosmic H₂. For coronene cations as prototypical Polycyclic Aromatic Hydrocarbon (PAH) molecules, the existence of magic numbers upon hydrogenation was uncovered experimentally. Quantum chemistry calculations show that hydrogenation follows a site-specific sequence leading to the appearance of cations having 5, 11, or 17 hydrogen atoms attached, exactly the magic numbers found in the experiments. For these closed-shell cations, further hydrogenation requires appreciable structural changes associated with a high transition barrier. Controlling specific hydrogenation pathways would provide the possibility to tune the location of hydrogen attachment and the stability of the system. The sequence to hydrogenate PAHs, leading to PAHs with magic numbers of H atoms attached, provides clues to understand that carbon in space is mostly aromatic and partially aliphatic in PAHs. PAH hydrogenation is fundamental to assess the contribution of PAHs to the formation of cosmic H₂.

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.

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.

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.