Lifetimes and wave functions of ozone metastable vibrational states near the dissociation limit in full symmetry approach (1607.04749v1)

Abstract: Energies and lifetimes (widths) of vibrational states above the lowest dissociation limit of $^{16}$O$_3$ were determined using a previously-developed efficient approach, which combines hyperspherical coordinates and a complex absorbing potential. The calculations are based on a recently-computed potential energy surface of ozone determined with a spectroscopic accuracy [J. Chem. Phys. {\bf 139}, 134307 (2013)]. The effect of permutational symmetry on rovibrational dynamics and the density of resonance states in O$_3$ is discussed in detail. Correspondence between quantum numbers appropriate for short- and long-range parts of wave functions of the rovibrational continuum is established. It is shown, by symmetry arguments, that the allowed purely vibrational ($J=0$) levels of $^{16}$O$_3$ and $^{18}$O$_3$, both made of bosons with zero nuclear spin, cannot dissociate on the ground state potential energy surface. Energies and wave functions of bound states of the ozone isotopologue $^{16}$O$_3$ with rotational angular momentum $J=0$ and 1 up to the dissociation threshold were also computed. For bound levels, good agreement with experimental energies is found: The RMS deviation between observed and calculated vibrational energies is 1~\cm. Rotational constants were determined and used for a simple identification of vibrational modes of calculated levels.