Electronic structure calculations of low-lying electronic states of O3

Abstract

Configuration-based multi-reference second order perturbation theory (CB-MRPT2) and multi-reference configuration interaction with single and double excitations (MRCISD) have been used to calculate the bending and dissociation potential energy curves (PECs) of ozone. Based on these PECs, equilibrium structures, vertical and adiabatic transition energies of the ground state and several low-lying excited states, as well as intersections and avoided crossings among the states displayed on the PECs are investigated. The energy separation of the open and ring structures and the dissociation energy of the ground state ¹A₁ are determined by reference-selected MRCISD. Furthermore, one-dimensional cuts along the dissociation reaction coordinate for the lowest four electronic states of O₃ with ¹A′ symmetry and possible pre-dissociations are studied. The Hartley band may be pre-dissociable, and the pre-dissociation limit is found to be 3871 cm⁻¹, which corresponds to symmetric stretching quanta n_ss ≈ 6.