Abstract
Phenyl isocyanide has about 1 eV more internal energy than phenyl cyanide (benzonitrile). At 193 nm the isomeric molecules are photodissociated into the same pair of radicals phenyl and cyanogen. The translational and internal state distribution of the CN radicals are very similar so that the bulk of the additional energy of the isocyanide appears in the phenyl ring. The dissociation is shown by several arguments to take place on a localized repulsive triplet surface. The lack of strong rotational excitation of the CN radicals shows that they are ejected more or less along the long axis of the molecule.
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