Top-down formation of ethylene from fragmentation of superhydrogenated polycyclic aromatic hydrocarbons

Abstract

Context.Fragmentation is an important decay mechanism for polycyclic aromatic hydrocarbons (PAHs) under harsh interstellar conditions and represents a possible formation pathway for small molecules such as H 2 , C 2 H 2 and C 2 H 4 . Aims. Our aim is to investigate the dissociation mechanism of superhydrogenated PAHs that undergo energetic processing and the formation pathway of small hydrocarbons. Methods. We obtain, experimentally, the mass distribution of protonated tetrahydropyrene (C 16 H + 15 , [py + 5H] + ) and protonated hexahydropyrene (C 16 H + 17 , [py+7H] + ) upon collision induced dissociation (CID). The IR spectra of their main fragments are recorded by infrared multiple-photon dissociation (IRMPD). Extended tight-binding (GFN2-xTB) based molecular dynamics simulations are performed in order to provide the missing structure information in experiment and identify fragmentation pathways. The pathways for fragmentation are further investigated at a hybrid-density functional theory (DFT) and dispersion corrected level. Results. A strong signal for loss of 28 mass units of [py + 7H] + is observed both in the CID experiment and the MD simulation, while [py + 5H] + shows negligible signal for the product corresponding to a mass loss of 28. The 28 mass loss from [py + 7H] + is assigned to the loss of ethylene (C 2 H 4 ) and a good fit between the calculated and experimental IR spectrum of the resulting fragment species is obtained. Further DFT calculations show favorable kinetic pathways for loss of C 2 H 4 from hydrogenated PAH configurations involving three consecutive CH 2 molecular entities. Conclusions. This joint experimental and theoretical investigation proposes a chemical pathway of ethylene formation from fragmentation of superhydrogenated PAHs. This pathway is sensitive to hydrogenated edges (e.g. the degree of hydrogenation and the hydrogenated positions). The inclusion of this pathway in astrochemical models may improve the estimated abundance of ethylene.

Ionic fragmentation products of benzonitrile as important intermediates in the growth of polycyclic aromatic hydrocarbons

“…Other studies have been looking into the destruction processes of astronomical relevant species to understand their stability and fragmentation processes. [17][18][19][20][21][22][23][24][25][26][27][28] Fragmentation processes are shown to play a role for the astronomically detected Buckminsterfullerenes C 60 , C 70 and C 60 + that are thought to be formed via top-down chemistry from large PAHs. 3,29,30 In a chemical environment like the interstellar medium the fragmentation and formation reactions are strongly intertwined.…”