Spectroscopy of ozone at the dissociation threshold: Quantum calculations of bound and resonance states on a new global potential energy surface

Abstract

The spectroscopy of O₃() near the O(³P) + O₂(³Σ_g⁻) threshold is investigated by means of quantum mechanical dynamics calculations (filter diagonalization with absorbing potential) on a global potential energy surface for the ground electronic state, ¹A′(¹A₁), obtained from multi-reference configuration interaction calculations. Most of the highly excited bound states and even a substantial number of the resonance states can be clearly assigned. As a result, the resonance widths show a pronounced state specificity with the longest lifetime being of the order of 1 ns—three orders of magnitude below the prediction of transition state theory.