The electronic properties of two room temperature persistent phases of germanium dioxide have been studied by means of experimental and theoretical techniques. We collected the Ge-K edge XANES spectra of these materials at the GILDA beamline of ESRF. The density of states of the two crystal phases obtained from fully periodic Hartree-Fock and density functional calculations is taken as the reference term to rationalise and assign the manifolds of the XANES spectra. Although this scheme requires a number of severe approximations we obtained a good overall agreement between experiment and theory. The topological analysis of the theoretical electron density distribution in the crystals gave further information regarding the electronic properties of germanium dioxide.
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