Journal article

Isomer-Specific Product Detection of Gas-Phase Xylyl Radical Rearrangement and Decomposition Using VUV Synchrotron Photoionization

Patrick Hemberger, Adam J Trevitt, Thomas Gerber, Edward Ross, Gabriel da Silva

JOURNAL OF PHYSICAL CHEMISTRY A | AMER CHEMICAL SOC | Published : 2014

Abstract

Xylyl radicals are intermediates in combustion processes since their parent molecules, xylenes, are present as fuel additives. In this study we report on the photoelectron spectra of the three isomeric xylyl radicals and the subsequent decomposition reactions of the o-xylyl radical, generated in a tubular reactor and probed by mass selected threshold photoelectron spectroscopy and VUV synchrotron radiation. Franck-Condon simulations are applied to augment the assignment of elusive species. Below 1000 K, o-xylyl radicals decompose by hydrogen atom loss to form closed-shell o-xylylene, which equilibrates with benzocyclobutene. At higher temperatures relevant to combustion engines, o-xylylene g..

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University of Melbourne Researchers

Grants

Awarded by Swiss Federal Office for Energy (BFE)


Awarded by Australian Research Council


Funding Acknowledgements

Experiments were carried out at the VUV beamline of the Swiss Light Source, Paul Scherrer Institute (PSI). The work was financially supported by the Swiss Federal Office for Energy (BFE Contract Number 101969/152433). A.J.T. and G.d.S. acknowledge funding support from the Australian Research Council (DP130100862, DP110103889, and FT130101304). Davide Ferri (PSI) is greatly acknowledged for his assistance to measure the infrared spectra. Useful discussions with Andras Bodi are gratefully acknowledged. Patrick Clark is mentioned for his contributions to the experimental work.