Theoretical investigation of product channels in the CH3O2 + Br reaction

Joseph S Francisco; John N Crowley

doi:10.1021/jp056794r

Theoretical investigation of product channels in the CH3O2 + Br reaction

J Phys Chem A. 2006 Mar 16;110(10):3778-84. doi: 10.1021/jp056794r.

Authors

Joseph S Francisco¹, John N Crowley

Affiliation

¹ Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA. francisc@purdue.edu

PMID: 16526662
DOI: 10.1021/jp056794r

Abstract

Several reaction pathways on the potential energy surface (PES) for the reaction of CH3O2 radicals with Br atoms are examined using both ab initio and density functional methods. Analysis of the PES suggests the presence of the stable intermediates CH3OOBr and CH3OBrO. CH3OOBr is calculated to be more stable than CH3OBrO by 9.7 kcal mol(-1) with a significant barrier preventing formation of CH3OBrO via isomerization of CH3OOBr. The relative importance of bi- and termolecular product channels resulting from the initially formed CH3OOBr adduct are assessed based on calculated barriers to the formation of CH2OO + HBr, CH3O + BrO, CH3Br + O2, and CH2O + HOBr.