Theoretical study of the ultraviolet photodissociation of ozone. Comparison with experiments

Abstract

We present a fully ab initio study of the photodissociation of the ozone molecule in the Hartley band. New ab initio potential energy surfaces PESs of the ground and B (1B2) states of ozone have been calculated with the complete-active space self-consistent field-single excitation configuration interaction double zeta+polarization method to describe the three-dimensional photodissociation process. The dissociation energy of the ground state and the vertical barrier height of the B PES are obtained to be 0.88 and 1.34 eV, respectively, in better agreement with the experimental values than previous calculations. The photodissociation process has been studied within the time-dependent wave-packet formulation, using hyperspherical coordinates. The calculations reported correspond to a total angular momentum value J=0. Detailed comparisons to experimental results are presented for the photodissociation spectrum, the autocorrelation function (AC), and the O2(1Δg) fragment rovibrational distributions. The recurrences observed in the AC function have been associated to a family of Feschbach resonances between the symmetric stretch and the bending motions.