Theoretical study of the thermal decomposition and isomerization of α-bromoethoxy radicals

A theoretical study of the thermal decomposition and isomerization channels of α-bromoethoxy radicals is reported. Geometry optimizations were carried out at the MP2(full)/6-311G(d,p) level of theory and energetics were calculated using G2MP2 theory. Bond scission, intramolecular three-center HBr elimination and isomerization processes have been examined. Energy-specific rate constants k(E) and thermal rate constants k(T) under atmospheric conditions, were evaluated using Rice–Ramsberger–Kassel–Marcus theory. The calculations indicate that C–Br bond scission is the dominant decomposition channel, providing theoretical evidence for the previous experimental result.