Structures, Vibrational Spectra, and Relative Energetics of CH₃BrO₃ Isomers

Abstract

The geometries, vibrational spectra, and relative energetics of CH 3 BrO 3 isomers have been examined using the B3LYP method in conjunction with various basis sets. The CH 3 OBrO 2 isomer is found to be the lowest energy structure among the isomers, with an estimated heat of formation of 10.6 kcal mol -1, at 0 K, as determined from G2 theory. The next lowest energy isomer is CH 3 OOOBr, which lies 5.6 kcal mol -1 above CH 3 OBrO 2 . The isomers with higher energies are CH 3 OOBrO and CH 3 BrO 3 . We have examined the implication of the formation of the CH 3 BrO 3 isomers from the atmospheric cross-reactions of the CH 3 O 2 and BrO radical species.