Origin of valence and core excitations in LiFePO(4) and FePO(4).

Electronic structures of LiFePO(4) and FePO(4) have been investigated using valence and core electron energy loss spectroscopy (EELS) supported by ab initio calculations. Valence electron energy loss spectra of FePO(4) are characterized by interband transitions found between 0 and 20 eV, which are not observed in LiFePO(4). Spectra are fully analysed using band structure calculations and calculated dielectric functions. In particular, we show that interband transitions observed in FePO(4) spectra originate from the states at the top of the valence band, which have mainly oxygen p character. From core-loss EELS, it is observed that the O-K edge in FePO(4) has a pre-edge peak below the threshold of the main O-K edge. This pre-edge peak is not observed in the O-K spectra of LiFePO(4). The position of the pre-edge peak is determined by a charge transfer process, which shifts the position of the iron 3d bands with respect to the conduction band. The intensity of the pre-edge peak is also determined by the changes in the hybridization of iron 3d and oxygen states as a result of extraction of lithium ions from the LiFePO(4) lattice. We show that the extraction of lithium ions from LiFePO(4) results in large changes in the electronic structure, such that FePO(4) can be considered to be a charge transfer insulator while LiFePO(4) is a typical Mott-Hubbard insulator.