A difficult assignment problem

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Abstract
From the experimental photoelectron spectra no definite assignment of the ionization potentials of O3 and SO2 could be deduced. The interpretation of the vibrational structure in the spectrum of O3 has also been controversial. The present work reports on a many-body calculation of the ionization potentials and the vibrational structure due to ionization of O3 and SO2. For the three lowest ionization potentials of both molecules the ordering a 1, a 2, b 2 is obtained. For O3, this assignment is in agreement with results obtained by Basch, but disagrees with the results of all other calculations (ΔSCF, CI, GVB-CI, LCAO-Xα, SW-Xα, INDO, etc.) reported in the literature. For SO2 no ab initio calculations have been reported which go beyond the Hartree-Fock level. We find that the stretching mode is excited in the a 2 band and the bending mode in the b 2 band of O3. The excitation of the bending mode dominates in all three bands of SO2.