PNNL

Abstract

The energy separation of the higher lying cation XPS binding energies, BEs, for MgO is examined. It is shown that the Hartree–Fock BEs overestimate the separation of the Mg BE(2s) and BE(2p), because an important many-body effect is neglected in the determination of the Hartree–Fock BEs. Once the many-body effect is taken into account, there is good agreement between theory and the XPS measurement. The character of this atomic many-body effect is established in terms of a nearly degenerate configuration that is needed to describe the wavefunction when an Mg 2s electron is ionized. The results provide additional evidence of the ionic character of the MgO crystal. Given the atomic character of the many-body effect, it is likely to apply also to the BE separations of other closed shell oxides.