A THEORETICAL-STUDY OF THE LOW-LYING EXCITED-STATES OF OZONE

A theoretical study has been performed on the five lowest excited stat es of the ozone molecule using multiconfigurational second-order pertu rbation theory (CASPT2). The predicted order of states is: (3)A(2) (T- 0 = 1.15 eV), B-3(2) (T-0 = 1.33 eV), B-3(1) (T-0 = 1.33 eV), (1)A(2) (T-0 = 1.44 eV) and B-1(1) (T-0 = 1.88 eV). Corresponding experimental data are: 1.18, 1.30, 1.45, 1.58, and 2.05 eV, respectively. Equilibr ium geometries, harmonic frequencies of symmetric vibrations, and vert ical excitation energies are also reported. The dissociation limit D-e for the ground state of ozone is found to be 1.08 eV, in agreement wi th the experimental value (1,13 eV). The calculations make use of a mo dified Fock operator in the CASPT2 theory. Relative energies of states with a different number of open shells are substantially improved. Th e modified CASPT2 method was checked by calculating spectroscopic cons tants of the oxygen molecule.