Electronic Structure of Molybdenum Dioxide Calculated by the Xα Method

The discrete variational‐Xα method employing a [Mo2O10]12− cluster is applied to electronic‐structure and density of states calculations of rutile family MoO2. Level profiles obtained are generally in good agreement with the optical conductivity data and observations by photoelectron spectroscopy. The splitting of the Mo 4d predominant levels just below the EF level is attributed to the formation of a partially filled Mo‐O(π*) type band which is lower in the binding energy by ≈︁ 0.7 eV than the completely filled Mo‐Mo(σ) type level or the nonbonding Mo 4d orbital, consistent with a recent UPS measurement. Intensity analyses of the XPS spectra indicate that the O 2p and Mo 4d predominant regions are substantially underestimated if the atomic‐subshell photoionization cross‐section is used.