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Dissociation of polycyclic aromatic hydrocarbons at high energy: MD/DFTB simulations versus collision experiments

Fragmentation paths, energy distribution and internal conversion: test on the pyrene cation

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Abstract

The whole process following collisions of polycyclic aromatic hydrocarbons (PAHs) with high energetic protons is modeled and compared to the experimental mass spectrum, allowing to propose a coherent scenario. Fragmentation of cationic pyrene \(\hbox {C}_{16}\hbox {H}_{10}^+\) is extensively studied by molecular dynamics simulations obtained by computing the electronic structure at the self-consistent-charge density functional-based tight binding (MD/SCC-DFTB) on-the-fly. An atomic model is used to quantify the energy transferred to the target after proton impact, and assuming fast internal conversion for the produced cations. From this model, after ionization, the molecules show a broad distribution of internal energy with a rough exponential decrease. This distribution is used as an input for further extensive MD/SCC-DFTB simulations. The good agreement between experimental and theoretical spectra globally validates the SCC-DFTB potential, the wide distribution of fragments corresponding to statistical dissociation. The scenario for both the internal energy deposited distribution and the fast internal conversion assumption is validated. Using these assumptions, dissociation is shown to occur within a few hundreds of picoseconds. Moreover, adjusting the experimental mass spectrum with the theoretical spectra obtained for the various internal energies nicely returns the distribution modeled from the atomic contributions, reinforcing the coherence of the global approach. This study lays the foundations for further synergistic theoretical and experimental studies that will be devoted to other PAHs and prebiotic molecules of astrophysical interest.

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Acknowledgements

This work is part of the SWEET project (Stellar Wind and Electron interactions on astrophysical molecules. Experiment and Theory), supported through the Grant NEXT No. ANR-10-LABX-0037 in the framework of the “Programme des Investissements d’Avenir.” We acknowledge the computing facility CALMIP at the Paul Sabatier University in Toulouse for generous allocation of computer resources. We also thank Georges Trinquier and Pierre Cafarelli for helpful discussions.

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  1. Lab. Chim. & Phys. Quant. LCPQ/IRSAMC, UMR5626 Université de Toulouse & CNRS, UT3-Paul Sabatier, 118 Route Narbonne, 31062, Toulouse, France

    A. Simon, M. Rapacioli & F. X. Gadéa

  2. Lab. Coll. Atom. & React. LCAR/IRSAMC, UMR5589 Université de Toulouse & CNRS, UT3-Paul Sabatier, 118 Route Narbonne, 31062, Toulouse, France

    J. P. Champeaux, P. Moretto Capelle & M. Sence

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Published as part of the special collection of articles “CHITEL 2017 - Paris - France”.

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Simon, A., Champeaux, J.P., Rapacioli, M. et al. Dissociation of polycyclic aromatic hydrocarbons at high energy: MD/DFTB simulations versus collision experiments. Theor Chem Acc 137, 106 (2018). https://doi.org/10.1007/s00214-018-2287-z

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