Joint product state distribution of coincidently generated photofragment pairs

Abstract

The joint product state distribution of coincident fragment pairs formed in the same elementary photodissociation process has been determined. This correlation between quantum state populations of two molecular products has been measured by high resolution Doppler spectroscopy in conjunction with level-specific detection of the ejected photofragments. One product molecule, formed in a specific quantum state, is excited by laser induced fluorescence and the wing of the corresponding Doppler profile is analyzed to determine the product state distribution of the partner fragment. In the photodissociation of jet-cooled hydrogen peroxide at 193 nm two OH partner radicals are formed with comparable angular momenta. For a specific rotation of one hydroxyl radical the product state distribution of the partner fragment is centered at about the same rotation with a width of only a few rotational quanta. The orbital angular momentum is of the order of 1 ℏ and the impact parameter is extremely small. Experimentally observed joint product state distribution and trajectory calculations on ab initio potential energy surfaces are in excellent agreement.