Electronic structure of Pr0.67Ca0.33MnO3 near the Fermi level studied by ultraviolet photoelectron and x-ray absorption spectroscopy

We have investigated the temperature-dependent changes in the near-EF occupied and unoccupied states of Pr0.67Ca0.33MnO3 which shows the presence of ferromagnetic and antiferromagnetic phases. The temperature-dependent changes in the charge and orbital degrees of freedom and associated changes in the Mn 3d–O 2p hybridization result in varied O 2p contributions to the valence band. A quantitative estimate of the charge transfer energy (ECT) shows a larger value compared to the earlier reported estimates. The charge localization causing the large ECT is discussed in terms of different models including the electronic phase separation.