Photoinduced polycyclic aromatic hydrocarbon dehydrogenation: The competition between H- and H2-loss

Abstract

PAHs constitute a major component of the interstellar medium carbon budget, locking up to 10--20% of the elemental carbon. Sequential fragmentation induced by energetic photons leads to the formation of new species, including fullerenes. However, the exact chemical routes involved in this process remain largely unexplored. In this work, we focus on the first photofragmentation steps, which involve the dehydrogenation of these molecules. For this, we consider a multidisciplinary approach, taking into account the results from experiments, DFT calculations, and modeling using dedicated Monte-Carlo simulations. By considering the simplest isomerization pathways --- i.e., hydrogen roaming along the edges of the molecule --- we are able to characterize the most likely photodissociation pathways for the molecules studied here. These comprise nine PAHs with clearly different structural properties. The formation of aliphatic-like side groups is found to be critical in the first fragmentation step and, furthermore, sets the balance of the competition between H- and H2-loss. We show that the presence of trio hydrogens, especially in combination with bay regions in small PAHs plays an important part in the experimentally established variations in the odd-to-even H-atom loss ratios. In addition, we find that, as PAH size increases, H2 formation becomes dominant, and sequential hydrogen loss only plays a marginal role. We also find disagreements between experiments and calculations for large, solo containing PAHs, which need to be accounted for. In order to match theoretical and experimental results, we have modified the energy barriers and restricted the H-hopping to tertiary atoms. The formation of H2 in large PAHs upon irradiation appears to be the dominant fragmentation channel, suggesting an efficient formation path for molecular hydrogen in PDRs.

arXiv comment17 pages, 13 figures, accepted for publication in A&A

References in corpus (12)

• Formation of buckminsterfullerene (C60) in interstellar space
• C${}_{60}$ in Reflection Nebulae
• Evolution of PAHs in photodissociation regions: Hydrogenation and charge states
• Laboratory formation of fullerenes from PAHs: Top-down interstellar chemistry
• Top-down formation of fullerenes in the interstellar medium
• Infrared Study of Fullerene Planetary Nebulae
• Theoretical evaluation of PAH dications properties
• H2 formation on PAHs in photodissociation regions: a high-temperature pathway to molecular hydrogen
• The detection of C60 in the well-characterized planetary nebula M1-11
• C${}_{60}$ in Photodissociation Regions
• PAH chemistry at eV internal energies. 2. Ring alteration and dissociation
• PAH chemistry at eV internal energies. 1. H-shifted isomers

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• Density Functional Theory Calculations on the Interstellar Formation of Biomolecules
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