Infrared action spectroscopy of the OD stretch fundamental and overtone transitions of the DOOO radical.
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 (nu(OD)) and overtone (2nu(OD)), respectively, of the trans-DOOO radical. Unstructured bands observed in both spectral regions are assigned to cis-DOOO. Nascent OD X(2)Pi 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 Pi(A') Lambda-doublets, which is interpreted as a signature of a planar dissociation. The energetically highest open OD X(2)Pi product channel implies an upper limit dissociation energy D0 < or = 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.
Derro
Erika L
EL
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
Sechler
Timothy D
TD
Murray
Craig
C
Lester
Marsha I
MI
D003903:Deuterium; D004735:Energy Transfer; D017665:Hydroxyl Radical / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D017550:Spectroscopy, Fourier Transform Infrared; D013237:Stereoisomerism
D017665:Hydroxyl Radical; D003903:Deuterium; D010100:Oxygen