Infrared action spectroscopy of the OD stretch fundamental and overtone transitions of the DOOO radical

Derro, E.L., Sechler, T.D., Murray, C. and Lester, M.I. (2008) Infrared action spectroscopy of the OD stretch fundamental and overtone transitions of the DOOO radical. Journal of Physical Chemistry A, 112(39), pp. 9269-9276. (doi: 10.1021/jp801232a)

Abstract

The DOOO radical has been produced by three-body association between OD and O₂ in a supersonic free-jet expansion and investigated using action spectroscopy, an IR−UV double-resonance technique. Partially rotationally structured bands observed at 2635.06 and 5182.42 cm⁻¹ are assigned to the OD stretch fundamental (νOD) and overtone (2ν_OD), respectively, of the trans-DOOO radical. Unstructured bands observed in both spectral regions are assigned to cis-DOOO. Nascent OD X²Π product state distributions following vibrational predissociation appear to be nearly statistical with respect to the degree of rotational excitation, but display a marked propensity for Π(A′) Λ-doublets, which is interpreted as a signature of a planar dissociation. The energetically highest open OD X²Π product channel implies an upper limit dissociation energy D₀ ≤ 1856 cm⁻¹ or 5.31 kcal mol−1. This value allows refinement of the upper limit D₀ of the atmospherically important HOOO isotopomer, suggesting that it is marginally less stable than previously thought.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Murray, Dr Craig
• Authors: Derro, E.L., Sechler, T.D., Murray, C., and Lester, M.I.
• Subjects: Q Science > QD Chemistry
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Journal of Physical Chemistry A
• ISSN: 1089-5639
• ISSN (Online): 1520-5215
• Published Online: 29 May 2008