Detailed theoretical and experimental description of normal Auger decay in O2

Abstract

The normal Auger electron spectrum of the O2 molecule is assigned in detail on the basis of ab initio valence configuration interaction (CI) wavefunctions. Potential energy curves of the ground state, the core-ionized states and the doubly charged final states are calculated and Auger decay rates are obtained with the one-centre approximation. Using the lifetime vibrational interference method, band shapes are obtained for all contributions to the Auger spectrum. The calculated Auger electron spectrum allows us to identify all features observed experimentally. Significant differences to previous assignments are reported. A quantitative simulation of the spectrum is given on the basis of a curve-fitting procedure, in which the energetic positions and intensities of the theoretical bands were optimized. Besides providing a basis for a refined analysis of the spectrum, the fit allows us to assess the accuracy of the calculation. As expected for this level of theory, the absolute accuracy of the valence CI energies is found to be about 0.3 eV. The inherent error of the one-centre transition rates is less than 5% of the most intense transition in the spectrum. The frequently questioned one-centre Auger transition rates are shown to be rather appropriate if applied with reasonable wavefunctions and if the vibrational band structure of the molecular spectrum is properly taken into account.