Calculations of the vibrational states up to dissociation threshold are carried out in the singly and doubly substituted molecules of ozone: 16O18O16O, 18O16O18O, 18O16O16O and 16O18O18O. This includes the usual vibrational states of ozone bound in a deep covalent well, but also the weakly bound floppy O…O2 complexes delocalized over the shallow van der Waals interaction region of the potential energy surface near dissociation threshold. Accurate variational approach is employed that uses the APH hyper-spherical coordinates and an accurate potential energy surface. Analysis of these spectra reveals noticeable deviations from the statistical factor of 2 for the ratio between the number of states in asymmetric and symmetric ozone molecules. It is found that, for the lower energy parts of spectra, the ratio is below 2 in the singly substituted ozone molecules, but it is above 2 in the doubly substituted ozone molecules. However, the upper parts of spectra, just below dissociation thresholds, exhibit a different behavior. In this energy range the singly and doubly substituted ozone molecules behave similar, with the ratio of states in asymmetric and symmetric ozone molecules being above 2 in both cases. This property may contribute to explanation of the mysterious η-effect in the ozone forming reaction that favors formation of the asymmetric ozone molecules.

Ratio of the number of states in asymmetric and symmetric ozone molecules deviates from the symmetry driven value of 2

2019 Spring National Meeting

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