Ab initio DFT studies of oxygen K edge NEXAFS spectra for the V2O3(0001) surface

Theoretical near edge X-ray absorption fine structure (NEXAFS) spectra describing oxygen 1s core excitation have been evaluated for the differently coordinated oxygen species appearing near the V2O3(0001) surface with half metal layer V′OV termination. Adsorption of oxygen above vanadium centers of the V′OV terminated surface (OtV′O termination) results in very strongly bound vanadyl oxygen, which has also been considered for core excitation in this study. The angle-resolved spectra are based on electronic structure calculations using ab initio density functional theory (DFT) together with model clusters. Experimental NEXAFS spectra for V2O3(0001) show a rather strong dependence of peak positions and relative intensities on the photon polarization direction. This dependence is well described by the present theoretical spectra and allows us to assign spectral details in the experiment to specific O 1s core excitations where final state orbitals are determined by the local binding environments of the differently coordinated oxygen centers. As a result, a combination of the present theoretical spectra with experimental NEXAFS data enables an identification of differently coordinated surface oxygen species at the V2O3(0001) surface.