THEORETICAL-STUDY OF THE ULTRAVIOLET PHOTODISSOCIATION OF OZONE - COMPARISON WITH EXPERIMENTS

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 (B-1(2)) 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 O-2((1) Delta(g)) 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.