Valence of “divalent” rare earth metals

It is generally recognized that light rare earths change their valence from 2 to 3 when forming a bulk metal while remaining divalent at the surface. However, performed DFT calculations ultimately indicate that the higher-binding-energy peaks in photoemission spectra (like the −5.3 eV peak for Sm), characteristic of the trivalent 4fn−15d1 configuration, correspond not to the ground state, but to excited states induced by radiation. This means that the trivalent state is not inherent for the bulk of divalent rare earths, and therefore they do not become trivalent.