Lifetimes and decay mechanisms of isotopically substituted ozone above the dissociation threshold: matching quantum and classical dynamics.

Abstract

Energies and lifetimes of vibrational resonances were computed for 18O-enriched isotopologue 50O3 = {16O16O18O and 16O18O16O} of the ozone molecule using hyperspherical coordinates and the method of complex absorbing potential. Various types of scattering resonances were identified, including roaming OO-O rotational states, the series corresponding to continuation of bound vibrational resonances of highly excited bending or symmetric stretching vibrational modes. Such a series become metastable above the dissociation limit. The coupling between the vibrationally excited O2 fragment and rotational roaming gives rise to Feshbach type resonances in ozone. Different paths for the formation and decay of symmetric 16O18O16O and asymmetric species 16O16O18O were also identified. The symmetry properties of the total rovibronic wave functions of the 18O-enriched isotopologues are discussed in the context of allowed dissociation channels.