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.
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
Erika L
EL
Derro
Timothy D
TD
Sechler
Craig
C
Murray
Marsha I
MI
Lester
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