Ab initio study for reactions of BrO with BrO, OBrO, and Br2O2

Reactions of BrO with BrO, OBrO, and Br2O2 have been investigated using ab initio method. Calculation at Quadratic Configuration Interaction, including single and double substitutions (QCISD)(T)/6-311++G(2df)//QCISD/6-311G*+ΔZPE level of theory suggests that BrO+BrO→Br+OBrO be endothermic by 3.8 kcal mol−1, and BrO+OBrO→Br2O+O2 be exothermic by 43.0 kcal mol−1, agreeing well with experimental measurements. The BrO self-reaction forming BrOO + Br and Br2O2 isomers is estimated to be exothermic by 6.8–22.0 kcal mol−1. Extractions of terminal Br from Br2O2 isomers by BrO yielding Br2O and BrO2 (i.e., BrOO or OBrO) are predicted to be exothermic by 15.1–21.0 kcal mol−1.