A theoretical study of the isomerization pathways for HBrO2 isomers

The geometries, vibrational spectra, and relative energetics of the HBrO2 isomers and their transition states have been examined using the quadratic configuration interaction method in conjunction with various basis sets. From the energetics of the dissociation and isomerization pathways of the HBrO2 isomers, it is found that the energy barrier for the isomerization of HOOBr to form HOBrO is high enough (67.2 kcal mol(-1)) to not allow the interconversion of HOOBr to HOBrO land vice verse). Thus, HOOBr and HOBrO are the intermediates that can be formed during the HO + BrO reaction. (C) 1999 Elsevier Science B.V. All rights reserved.