Quasiclassical and quantum mechanical modeling of the breakdown of the axial recoil approximation observed in the near threshold photolysis of IBr and Br2

The photodissociations of jet-cooled IBr and Br2 molecules have been investigated using high resolution ion imaging methods, at excitation energies just above the thresholds for forming, respectively, I(2P3/2o)+Br(2P3/2o) and Br(2P3/2o)+Br*(2P1/2o) products from parent molecules in their v″=0 levels. For such molecules, we observe in both cases, that fragments with larger recoil velocities have markedly reduced angular anisotropy, whereas those from photolysis of IBr molecules with v″=1 show an essentially constant, limiting anisotropy. Given the monochromaticity of the photolysis radiation, increased recoil velocity of fragments resulting from photolysis of v″=0 molecules can only be derived from increased parent internal (rotational) energy. The measurements thus provide a particularly clear and direct observation of the breakdown of the axial recoil approximation as applied to the photodissociation of a diatomic molecule, and have been modeled, quantitatively, using both quantum and semiclassical methods together with the best available potential energy curves for the relevant excited states of IBr and Br2.