Derro, E.L., Murray, C., Sechler, T.D. and Lester, M.I. (2007) Infrared action spectroscopy and dissociation dynamics of the HOOO radical. Journal of Physical Chemistry A, 111(45), pp. 11592-11601. (doi: 10.1021/jp0760915)
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Abstract
The HOOO radical has long been postulated to be an important intermediate in atmospherically relevant reactions and was recently deemed a significant sink for OH radicals in the tropopause region. In the present experiments, HOOO radicals are generated in a pulsed supersonic expansion by the association of O<sub>2</sub> and photolytically generated OH radicals, and the spectral signature and vibrational predissociation dynamics are investigated via IR action spectroscopy, an IR-UV double resonance technique. Rotationally resolved IR action spectra are obtained for trans-HOOO in the fundamental (ν<sub>OH</sub>) and overtone (2ν<sub>OH</sub>) OH stretching regions at 3569.30 and 6974.18 cm<sup>-1</sup>, respectively. The IR spectra exhibit homogeneous line broadening, characteristic of a ∼26-ps lifetime, which is attributed to intramolecular vibrational redistribution and/or predissociation to OH and O<sub>2</sub> products. In addition, an unstructured feature is observed in both the OH fundamental and overtone regions of HOOO, which is likely due to cis-HOOO. The nascent OH X<sup>2</sup>Π, v = 0 or v = 1, products following vibrational predissociation of HOOO, ν<sub>OH</sub> or 2ν<sub>OH</sub>, respectively, have been investigated using saturated laser-induced fluorescence measurements. A distinct preference for population of Π(A‘) Λ-doublets in OH was observed and is indicative of a planar dissociation of trans-HOOO in which the symmetry of the bonding orbital is maintained.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Murray, Dr Craig |
| Authors: | Derro, E.L., Murray, C., Sechler, T.D., and Lester, M.I. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Journal of Physical Chemistry A |
| ISSN: | 1089-5639 |
| Published Online: | 24 October 2007 |
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