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, includin g single and double substitutions (QCISD)(T)/6-311++G(2df)//QCISD/6-311G*+D elta ZPE level of theory suggests that BrO+BrO --> Br+OBrO be endothermic b y 3.8 kcal mol(-1), and BrO + OBrO --> Br2O + O-2 be exothermic by 43.0 kca l mol(-1), agreeing well with experimental measurements. The BrO self-react ion forming BrOO + Br and BT2O2 isomers is estimated to be exothermic by 6. 8-22.0 kcal mol(-1). Extractions of terminal Br from Br2O2 isomers by BrO y ielding Br2O and BrO2 (i.e., BrOO or OBrO) are predicted to be exothermic b y 15.1-21.0 kcal mol(-1). (C) 2001 Elsevier Science B.V. All rights reserve d.