Fully relativistic analysis of the covalence effects for the isoelectronic 3d3 ions (Cr3+, Mn4+, Fe5+) in SrTiO3

Fully relativistic calculations of the energy levels, absorption spectra, molecular orbitals (MO) compositions, covalence effects and energies of the charge transfer (CT) transitions for three isoelectronic ions Cr3+, Mn4+, Fe5+ in the SrTiO3 (STO) crystal have been performed. The recently developed first-principles approach to the analysis of the absorption spectra based on the first principles discrete variational multi-electron method (DV-ME) (K. Ogasawara et al., Phys. Rev. B 64 (2001) 115413) was used in the calculations. As a result, energy levels of the above ions, their absorption spectra and energies of the lowest CT transitions were all calculated. By performing analysis of the MO population, it was shown that the degree of covalence of the chemical bonds between 3d ions and oxygen ions in SrTiO3 increases in the following order: Cr3+→Mn4+→Fe5+, whereas the CT energies monotonically decrease in the same order.