ABSTRACT
Electronic excitations in the correlated metal BaTi(0.02)V(0.98)S(3) have been studied using resonant inelastic soft x-ray scattering at the V L edge. The intensities of the intra-atomic d-d(*) excitations and the elastic x-ray scattering feature are found to be temperature dependent, with the intensity increasing with decreasing temperature until saturation is reached near 100 K. The behavior of the spectral features is interpreted as evidence of a shift in the 3d electrons from more band-like states at higher temperature to more localized states at low temperature.
Subject(s)
Barium/chemistry , Electrons , Sulfur/chemistry , Titanium/chemistry , Vanadium/chemistry , X-Ray Diffraction , Crystallography, X-Ray , Elasticity , Models, Molecular , Molecular Conformation , Temperature , X-Ray Absorption SpectroscopyABSTRACT
Structural distortions in post-transition metal oxides are often explained in terms of the influence of sp hybrid "lone pairs." Evidence is presented here showing that this model must be revised. The electronic structures of prototypically distorted alpha-PbO and alpha-Bi2O3 have been measured by high-resolution x-ray photoemission and soft x-ray emission spectroscopies. In contrast with the expectations of the lone pair model, a high density of metal 6s states is observed at the bottom of the valence band. The measurements are consistent with the results of density functional theory calculations.