Abstract
The photodissociation of ClO radicals produced photolytically in a molecular beam was studied at 248 nm using photofragment translational energy spectroscopy. Excitation into the ClO absorption continuum to the blue of the structured region of the ClO(A2Π ←X2Π) spectrum led to dominant (∼97%) formation of Cl(2P3/2) + O(1D2) with negligible (<0.5%) production of Cl(2P1/2) + O(1D2). The photofragment anisotropy parameter (β) was measured to be 1.2 ± 0.2 for the dominant Cl(2P3/2) + O(1D2) channel, significantly less than the limiting value of 2.0 expected for the parallel ClO (A2Π ← X2Π) transition. This indicates that, in the ClO continuum region near 248 nm, absorption to an as yet uncharacterized electronic state [probably B(2Σ+)] carries ∼30% of the oscillator strength. This state, like ClO(A2Π), dissociates primarily to Cl(2P3/2) + O(1D2). A second minor photodissociation channel, accounting for approximately 3% of the ClO absorption cross section, leads to production of Cl(2P1/2) + O(3PJ). As in the photodissociation of ClO below the A2Π convergence limit, this minor channel probably involves predissociation of ClO(A2Π) by one or more as yet uncharacterized repulsive electronic surfaces.
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