Hole counts from X-ray absorption spectra

The interpretation of X-ray absorption spectra in terms of electronic struc ture has long been of interest. Hole counts derived from such spectra are o ften interpreted in terms of free-atom occupation numbers or Mulliken count s. It is shown here, however, that renormalized-atom (RA) and cellular coun ts are better choices to characterize the configuration of occupied electro n states in molecules and condensed matter. A projection-operator approach is introduced to subtract delocalized states and to determine quantitativel y such hole counts from X-ray absorption spectra. The described approach is based on multiple-scattering theory (MST) and on atomic calculations of a smooth transformation relating the X-ray absorption spectra to local projec ted densities of states (LDOS). Theoretical tests for the s and d electrons in transition metals show that the approach works well.