Band structure analysis of resonant photoemission in ZrO2

A detailed analysis of the density of states of the cubic phase of ZrO2 ove r a broad energy range, calculated by means of the linear muffin-tin orbita l method, showed that the two experimental resonances at 39 and 45 eV could be explained in terms of electronic transitions within the local density a pproximation. The resonance at 39 eV is assigned to electronic transitions from the 4p to the 4d status of Zr. The calculated bulk 4p --> 4d transitio ns are about 36 eV. The discrepancy with experiment is due to out. underest imation of the band gap by about 3 eV. The higher energy resonance at 45 eV is assigned to electronic transitions From Zr 4p states to empty hybridize d (Zr 4s and O 2p) conduction band states dominated by an O 2p contribution . Our calculation found this latter resonance at 3 eV below the experimenta l value. Here again the discrepancy is due to a much smaller calculated ban d gap.