Valence band electronic structure of Nd1−xYxMnO3 using X-ray absorption, photoemission and GGA + U calculations

Abstract

The electronic structures of Nd1−xYxMnO3 (x=0–0.5) were studied using X-ray absorption near-edge structure (XANES) at the Mn L3,2- and O K-edge along with valence-band photoemission spectroscopy (VB-PES). The systematic increase in white-line intensity of the Mn L3,2-edge with doping, suggests a decrease in the occupancy of Mn 3d orbitals. The O K-edge XANES shows a depletion of unoccupied states above the Fermi energy. The changes in the O K-edge spectra due to doping reflects an increase in the Jahn–Teller distortion. The VB-PES shows broadening of the features associated with Mn 3d and O 2p hybridized states and the shift of these features to a slightly higher binding energy in agreement with our GGA+U calculations. The system shows a net shift of the occupied and unoccupied states away from the Fermi energy with doping. The shift in theoretical site-projected density of states of x=0.5 composition with respect to x=0 suggest a subtle change from a charge transfer to Mott–Hubbard type insulator.