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Register a new userAstrochemical relevance of VUV ionization of large PAH cations
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Authors
Gabi Wenzel
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As a part of interstellar dust, polycyclic aromatic hydrocarbons (PAHs) are processed by the interaction with vacuum ultraviolet (VUV) photons that are emitted by hot young stars. This interaction leads to the emission of the well-known aromatic infrared bands but also of electrons, which can significantly contribute to the heating of the interstellar gas.Our aim is to investigate the impact of molecular size on the photoionization properties of cationic PAHs.Methods. Trapped PAH cations of sizes between 30 and 48 carbon atoms were submitted to VUV photons in the range of 9 to 20 eV from the DESIRS beamline at the synchrotron SOLEIL. All resulting photoproducts including dications and fragment cations were mass-analyzed and recorded as a function of photon energy.Photoionization is found to be predominant over dissociation at all energies, which differs from an earlier study on smaller PAHs. The photoionization branching ratio reaches 0.98 at 20 eV for the largest studied PAH. The photoionization threshold is observed to be between 9.1 and 10.2 eV, in agreement with the evolution of the ionization potential with size. Ionization cross sections were indirectly obtained and photoionization yields extracted from their ratio with theoretical photoabsorption cross sections, which were calculated using time-dependent density functional theory. An analytical function was derived to calculate this yield for a given molecular size.Large PAH cations could be efficiently ionized in H i regions and provide a contribution to the heating of the gas by photoelectric effect. Also, at the border of or in H ii regions, PAHs could be exposed to photons of energy higher than 13.6 eV. Our work provides recipes to be used in astronomical models to quantify these points.
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A gas-phase optical spectrum of a large polycyclic aromatic hydrocarbon (PAH) cation - C78H26 +- in the 410-610 nm range is presented. This large all-benzenoid PAH should be large enough to be stable with respect to photodissociation in the harsh conditions prevailing in the interstellar medium (ISM). The spectrum is obtained via multi-photon dissociation (MPD) spectroscopy of cationic C78H26 stored in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) cell using the radiation from a mid-band optical parametric oscillator (OPO) laser. The experimental spectrum shows two main absorption peaks at 431 nm and 516 nm, in good agreement with a theoretical spectrum computed via time-dependent density functional theory (TD-DFT). DFT calculations indicate that the equilibrium geometry, with the absolute minimum energy, is of lowered, nonplanar C2 symmetry instead of the more symmetric planar D2h symmetry that is usually the minimum for similar PAHs of smaller size. This kind of slightly broken symmetry could produce some of the fine structure observed in some diffuse interstellar bands (DIBs). It can also favor the folding of C78H26 + fragments and ultimately theformation of fullerenes. This study opens up the possibility to identify the most promising candidates for DIBs amongst large cationic PAHs.
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 radiofrequency 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 hydrogenation, barrier heights of 72 +- 6 meV and 40 +- 10 meV, respectively are found which is 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.
We have measured fragmentation branching ratios of neutral CnH and CnH+ cations produced in high velocity (4.5 a.u) collisions between incident CnH+ cations and helium atoms. Electron capture gives rise to excited neutral species CnH and electronic excitation to excited cations CnH+. Thanks to a dedicated set-up, based on coincident detection of all fragments, the dissociation of the neutral and cationic parents were recorded separately and in a complete way. For the fragmentation of CnH, the H-loss channel is found to be dominant, as already observed by other authors. By contrast, the H-loss and C-loss channels equally dominate the two-fragment break up of CnH+ species. For these cations, we provide the first fragmentation data (n > 2). Results are also discussed in the context of astrochemistry.
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