Theory of x-ray absorption spectroscopy for ferrites

Abstract

The theoretical calculation of the interaction of electromagnetic radiation with matter remains a challenging problem for contemporary $ab$ $initio$ electronic structure methods, in particular for x-ray spectroscopies. This is not only due to the strong interaction between the core-hole and the photo-excited electron, but also due to the elusive multiplet effects that arise from the Coulomb interaction among the valence electrons. In this work we report a method based on density-functional theory in conjunction with multiplet ligand-field theory to investigate various core-level spectroscopies, in particular x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD). The developed computational scheme is applied to the $L_{2,3}$ XAS edges of magnetite (Fe$_3$O$_4$) as well as cobalt ferrite (CoFe$_2$O$_4$) and nickel ferrite (NiFe$_2$O$_4$) and the corresponding XMCD spectra. The results are in overall good agreement with experimental observations, both regarding the XAS $L_2$/$L_3$ branching ratio, the peak positions as well as the relative intensities. The agreement between theory and experiment is equally good for XAS and the XMCD spectra, for all studied systems. The results are analyzed in terms of $e_g$ and $t_{2g}$ orbitals contributions and the importance of optimizing the Slater parameters. The analysis also highlights the strong effect of the $2p$-$3d$ interaction in x-ray spectroscopy.