Journal article

Using distonic radical ions to probe the chemistry of key combustion intermediates: The case of the benzoxyl radical anion

C Li, AKY Lam, GN Khairallah, JM White, RAJ O'Hair, G Da Silva

Journal of the American Society for Mass Spectrometry | SPRINGER | Published : 2013

Abstract

The benzoxyl radical is a key intermediate in the combustion of toluene and other aromatic hydrocarbons, yet relatively little experimental work has been performed on this species. Here, a combination of electrospray ionization (ESI), multistage mass spectrometry experiments, and density functional theory (DFT) calculations are used to examine the formation and fragmentation of a benzoxyl (benzyloxyl) distonic radical anion. Excited 4-carboxylatobenzoxyl radical anions were produced via two methods: (1) collision induced dissociation (CID) of the nitrate ester 4-(nitrooxymethyl)benzoate, -O 2CC6H4CH2ONO2, and (2) reaction of ozone with the 4-carboxylatobenzyl radical anion, -O 2CC6H4CH2 •. I..

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Grants

Awarded by Australian Research Council


Funding Acknowledgements

The authors thank the Australian Research Council (ARC) for financial support via the ARC Centre of Excellence in Free Radical Chemistry and Biotechnology (R.A.J.O.) and Discovery Project DP110103889 (G.dS.). This work was also supported by the University of Melbourne Interdisciplinary Seed Funding initiative. The authors gratefully acknowledge the generous allocation of computing time from both the Victorian Partnership for Advanced Computing (VPAC) and the National Computational Infrastructure National Facility (NCI-NF). The authors would also thank the ARC and VICS for funding of the LTQ FT hybrid mass spectrometer instrument.