Symmetry role on the preedge X—ray absorption fine structure at the metal K edge

The preedge features in a system with “even”symmetry,apart from quadrupolar transition contribution,are mainly dipolar in character,associated with the existence of unoccupied states made up of mixed cation-4p with higher-neighboring cation-3d orbitals,and reflect the density of states due to the medium-range order of the system.In “odd“symmetry materials these preedge features ate the result of a transition from the ls to a final density of states of p symmetry due to an unsymmetrical mixing of the ligand wave functions with the central cation 3d orbitals,similar to atetrahedral configuration.These results are validated for Fe as a photoabsorber by comparing XAS spectra of Fe2SiO4(fayalite) to ab initio full multiple scattering calculations at the fe K edge,but pertain to all systems containing sixfold-coordinated cations.