Theoretical analysis of the O(1s) binding-energy shifts in alkaline-earth oxides: Chemical or electrostatic contributions.

Abstract

We report results from ab initio cluster-model calculations on the O(1s) binding energy (BE) in the alkaline-earth oxides, MgO, CaO, SrO, and BaO; all these oxides have a cubic lattice structure. We have obtained values for both the initial- and final-state BE's. A simple point-charge model, where an ${\mathrm{O}}^{2\mathrm{\ensuremath{-}}}$ anion is surrounded by point charges, accounts for the observed shift in the O(1s) BE by about 2.5 eV to lower energy going from MgO (largest BE) to BaO (smallest BE). This point-charge model only describes the effect of the Madelung potential at the 1s ionized ${\mathrm{O}}^{2\mathrm{\ensuremath{-}}}$ anion; it does not allow any covalent bonding between the metal (M) cations and the oxygen anions. Once the effect of the ${\mathrm{O}}^{2}$\ensuremath{\rightarrow}${\mathit{M}}^{2+}$ covalent bonding is included explicitly by using ${\mathrm{O}}_{\mathit{m}}$${\mathit{M}}_{\mathit{n}}$ cluster models of the MO crystal, the trend in the O(1s) BE to smaller values for heavier metals does not change significantly. This shows that the main contribution to the shift is not the different amount of covalent mixing in the alkaline-earth oxides but rather the change in the Madelung potential along the group.