Molecular Photodissociation Dynamics Revealed by Multiphoton Ionisation Spectroscopy

This article highlights the utility of multiphoton ionisation Spectroscopy to studies of the predissociation dynamics of Rydberg states in small polyatomic molecules. Predissociation from various of the excited states of H 2 O, H 2 S and their respective deuterated analogues is demonstrated to be a sensitive function of parent rotational level and to be critically affected by H ↔ D isotopic substitution and by accidental near resonances with more heavily predissociated “doorway” states which provide more efficient coupling into the background continuum of dissociative levels.