First-principle calculations analysis of ELNES splitting for Mn3O4 spinels related to atomic local symmetry

By using a real space multiple scattering method (FEFF code) with a 2×2×2 cluster model, we investigated the effects of characteristic Jahn–Teller distortion on the electron energy loss near-edge structure (ELNES) of Mn3O4 spinel. In particular, we examined a correlation between the characteristics of the density of state and the ELNES spectral feature as a function of Jahn–Teller distortion. To this end, we introduced a geometrical variation approach to an Mn3O4 cluster model containing both Mn3+ and Mn2+ sites. Upon a prominent Jahn–Teller distortion of the Mn3+-octahedral site, we resolved the associated spectral features of Mn, comprising three peaks that merged upon increasing the symmetry of octahedral site from tetragonal (D4h) to cubic (Oh). We have also investigated the interplay between the Mn L-edge and corresponding O K-edge spectra. - Highlights: • ELNES of Mn3O4 is simulated using first-principles calculations. • The Jahn–Teller effect is studied in a qualitative manner by using a geometrical variation method. • A correlation between the density of state and the ELNES via the Jahn–Teller distortion is presented. • Both Mn2+ and Mn3+ sites contribute to the first peak. • The Mn3+ sites are further responsible for the second and third peaks on the ELNES