Photofragment vector correlations as a probe of K‐scrambling in unimolecular dissociation

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Abstract
We discuss the relationship between fragment‐rotational polarization and the extent of K‐mixing in an energized molecule undergoing unimolecular dissociation at fixed energy and angular momentum. Accurate measurements of the second Legendre moment of the v · j angular correlation are presented for the CN fragments produced in the photoinitiated dissociation of NCCN at 193 nm. as determined by Doppler spectroscopy using a transient frequency modulation technique. The strength of the correlation significantly exceeds what would be observed if all K states of the dissociating molecule were equally represented.