First-Principles Calculation of Ligand Field Parameters for L-Edge Spectra of Transition Metal Sites of Arbitrary Symmetry

Recently we have proposed a simple method for obtaining the parameters of a ligand field multiplet model for L-edge spectra calculations from density functional theory. Here we generalize the method to systems where the metal site has arbitrary point symmetry. The ligand field-induced splitting of the metal d-level becomes a hermitian matrix with cross-terms between the different d-orbitals. The anisotropy of the covalency is fully taken into account and it rescales the electron-electron interaction and the oscillator strength in an orbital-dependent way. We apply the method to polarization-dependent V L-edge spectra of vanadium pentoxide and obtain very good agreement with the experiment.

Automated summary

Recently, we have proposed a simple method to calculate the parameters of a ligand field multiplet model for L-edge spectra calculations using density functional theory. In this study, we extend the method to systems with arbitrary point symmetry at the metal site. The ligand field-induced splitting of the metal d-level is represented as a hermitian matrix with cross-terms between different d orbitals. The anisotropy of covalency is taken into account, leading to rescaling of electron-electron interaction and oscillator strength in an orbital-dependent manner. We apply the method to polarization-dependent V L-edge spectra of vanadium pentoxide and achieve excellent agreement with experimental results.