Volume 641, September 2020
|Number of page(s)||10|
|Section||Interstellar and circumstellar matter|
|Published online||16 September 2020|
Astrochemical relevance of VUV ionization of large PAH cations★
Institut de Recherche en Astrophysique et Planétologie (IRAP), Université de Toulouse (UPS), CNRS, CNES,
9 Avenue du Colonel Roche,
2 Synchrotron SOLEIL, L’Orme des Merisiers, 91192 Saint Aubin, Gif-sur-Yvette, France
3 INRAE, UAR1008, Transform Department, Rue de la Géraudière, BP 71627, 44316 Nantes, France
4 Laboratoire de Chimie et Physique Quantiques (LCPQ/IRSAMC), Université de Toulouse (UPS), CNRS, 118 Route de Narbonne, 31062 Toulouse, France
5 Istituto Nazionale di Astrofisica – Osservatorio Astronomico di Cagliari, Via della Scienza 5, 09047 Selargius (CA), Italy
6 Laboratoire Collisions Agrégats Réactivité (LCAR/IRSAMC), Université de Toulouse (UPS), CNRS, 118 Route de Narbonne, 31062 Toulouse, France
7 Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
Accepted: 1 July 2020
Context. As part of interstellar dust, polycyclic aromatic hydrocarbons (PAHs) are processed by an interaction with vacuum ultraviolet (VUV) photons emitted by hot stars. This interaction leads to the emission of not only the well-known aromatic infrared bands, but also electrons, which can significantly contribute to the heating of the interstellar gas.
Aims. 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 9–20 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.
Results. Photoionization is found to be predominant over dissociation at all energies, which differs from the conclusions of 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.
Conclusions. Large PAH cations could be efficiently ionized in H I regions and contribute to the heating of the gas by the 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.
Key words: astrochemistry / methods: laboratory: molecular / molecular processes / ISM: molecules / dust, extinction / ultraviolet: ISM
The dataset associated with this work can be found under https://doi.org/10.5281/zenodo.3899775
© G. Wenzel et al. 2020
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