Unimolecular decomposition of aromatic bicyclic alkoxy radicals and their acyclic radicals Academic Article

abstract

• The unimolecular decomposition of bicyclic alkoxy radicals and their subsequent ring-cleavage acyclic radicals from the OH-initiated reactions of toluene is investigated by means of theoretical quantum chemistry methods. The reaction and activation energies of ring-cleavage of the bicyclic alkoxy radicals are in the ranges of -45.9 to -54.5 kcal mol-1 and 5.5-11.3 kcal mol-1, respectively. The activation energies of C-C bond cleavage of the acyclic radicals are in the range of 2.5-27.0 kcal mol-1. Kinetic calculations employing RRKM/ME formalism have been performed to assess the fate of chemically excited acyclic radicals for prompt decomposition or stabilization. The results indicate that the favorable decomposition pathways of the bicyclic alkoxy radicals correspond to the formation of dicarbonyl compounds along with glyoxal and methylglyoxal. 2006 Elsevier B.V. All rights reserved.

authors

• Zhang, Renyi

published proceedings

• CHEMICAL PHYSICS LETTERS

author list (cited authors)

• Suh, I., Zhao, J., & Zhang, R.

citation count

• 22

complete list of authors

• Suh, Inseon||Zhao, Jun||Zhang, Renyi

publication date

• December 2006

publisher

• Elsevier  Publisher

published in

• CHEMICAL PHYSICS LETTERS  Journal

Digital Object Identifier (DOI)

• 10.1016/j.cplett.2006.08.145

start page

• 313

end page

• 320

volume

• 432

issue

• 1-3

URL

• http%3A%2F%2Fdx.doi.org%2F10.1016%2Fj.cplett.2006.08.145