Computational studies on the thermal decomposition and isomerization of CHBr2O radical

The unimolecular decomposition study of dibromomethoxy radical, CHBr2O, and its isomeric hydroxy dibromomethyl radical, CBr2OH, is carried out using ab initio electronic molecular structure methods. Three kinds of reaction pathways are examined, C-H and C-Br bond scissions, intramolecular three-center HBr elimination and isomerization. Based on the ab initio results, energy-specific rate coefficients k(E) and thermal rate constants k(T,P) are evaluated using RRKM theory and master equation numerical analysis. Relevance to existing experimental evidence is discussed.