Infrared spectroscopy of the benzylium-like (and tropylium-like) isomers formed in the –H dissociative ionization of methylated PAHs

Wenzel, Gabi; Simon, Aude; Banhatti, Shreyak; Jusko, Pavol; Schlemmer, Stephan; Brünken, Sandra; Joblin, C.

doi:10.1016/j.jms.2022.111620

Cited by 10 publications

(11 citation statements)

References 52 publications

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“…A variety of studies has been investigating the fragmentation processes of astronomical relevant molecules in detail ranging from theoretical [29][30][31] to experimental studies using dissociative ionization and infrared spectroscopy [32][33][34][35][36][37] or imaging Photoelectron-Photoion-Coincidence (iPEPICO) spectroscopy [38][39][40] . By using a combination of techniques, some of these studies have provided structural information of the fragment ions.…”

Section: Introductionmentioning

confidence: 99%

Fingerprinting fragments of fragile interstellar molecules: dissociation chemistry of pyridine and benzonitrile revealed by infrared spectroscopy and theory

et al. 2023

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Section: Introductionmentioning

confidence: 99%

Fingerprinting fragments of fragile interstellar molecules: dissociation chemistry of pyridine and benzonitrile revealed by infrared spectroscopy and theory

et al. 2023

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“…This might be due to different effects including limitations of the anharmonic calculations that provide only a very basic treatment of resonances, e.g., Mulas et al 52 and a possible role of the Ne tag on the IRPD spectrum. 53…”

Section: Reference Spectramentioning

confidence: 99%

Formation of the acenaphthylene cation as a common C₂H₂-loss fragment in dissociative ionization of the PAH isomers anthracene and phenanthrene

Banhatti

Rap

Simon

et al. 2022

Phys. Chem. Chem. Phys.

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“…2 (f) is already good, we refrain from constructing a blended IR spectrum composed of contributions from numerous isomers. Such an attempt was done by Wenzel et al (2022) in another H-functionalized pyrene system and was found challenging as it requires choices to be made for the number of isomers to include and for their relative weights. Based on the good match between Fig.…”

Section: Confirmation Of the Ethylene Formationmentioning

confidence: 99%

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

Tang

Simonsen

Jaganathan

et al. 2022

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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.

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Infrared spectroscopy of the benzylium-like (and tropylium-like) isomers formed in the –H dissociative ionization of methylated PAHs

Cited by 10 publications

References 52 publications

Fingerprinting fragments of fragile interstellar molecules: dissociation chemistry of pyridine and benzonitrile revealed by infrared spectroscopy and theory

Fingerprinting fragments of fragile interstellar molecules: dissociation chemistry of pyridine and benzonitrile revealed by infrared spectroscopy and theory

Formation of the acenaphthylene cation as a common C₂H₂-loss fragment in dissociative ionization of the PAH isomers anthracene and phenanthrene

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

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Infrared spectroscopy of the benzylium-like (and tropylium-like) isomers formed in the –H dissociative ionization of methylated PAHs

Cited by 10 publications

References 52 publications

Fingerprinting fragments of fragile interstellar molecules: dissociation chemistry of pyridine and benzonitrile revealed by infrared spectroscopy and theory

Fingerprinting fragments of fragile interstellar molecules: dissociation chemistry of pyridine and benzonitrile revealed by infrared spectroscopy and theory

Formation of the acenaphthylene cation as a common C2H2-loss fragment in dissociative ionization of the PAH isomers anthracene and phenanthrene

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

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Formation of the acenaphthylene cation as a common C₂H₂-loss fragment in dissociative ionization of the PAH isomers anthracene and phenanthrene