An examination of the reaction pathways for the HOOOBr and HOOBrO complexes formed from the HO{sub 2} + BrO reaction
The geometries, vibrational spectra, and relative energetics of the HBrO{sub 3} isomers (HOOOBr and HOOBrO) and their transition states have been examined by using the quadratic configuration interaction method in conjunction with various basis sets. From the dissociation energies of the HBrO{sub 3} isomers, it is found that the most energetically favorable process during the HO{sub 2} + BrO reaction pathway is the formation of HOOBrO as an intermediate, and its eventual dissociation into HOBr and O{sub 2}, due to the very low energy barrier (2.8 kcal mol{sup {minus}1}) involved. The HOOOBr species, if formed as an intermediate, will be more likely to dissociate into HBr + O{sub 3} rather than HOBr + O{sub 2}, as the energy barrier for the latter process is quite high (26.4 kcal mol{sup {minus}1}) relative to the energy barrier for the HOOOBr {r{underscore}arrow} HBr + O{sub 3} dissociation process.
- Research Organization:
- Purdue Univ., West Lafayette, IN (US)
- OSTI ID:
- 20001099
- Journal Information:
- Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 40 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
- Country of Publication:
- United States
- Language:
- English
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