Hard x-ray photoemission spectroscopy of the ferrimagnetic series Gd6(Mn1−xFex)23

We study the evolution of the electronic structure of the intermetallic series ${\mathrm{Gd}}₆{({\mathrm{Mn}}_{1\ensuremath{-}x}{\mathrm{Fe}}_x)}₂₃, x=0.0--0.75$, which shows nonmonotonic ferrimagnetic ordering temperatures ${T}_C$ but with a systematic reduction of the total bulk magnetization upon increasing Fe content, $x$. We have carried out hard x-ray photoemission spectroscopy to elucidate the relation between electronic structure and properties of the series. The Gd $3d$ and Gd $4d$ core-level spectra indicate trivalent ${\mathrm{Gd}}³⁺$ multiplets in the intermediate-coupling scheme with features due to $L\text{\ensuremath{-}}S$ and $j\text{\ensuremath{-}}J$ coupling. The Fe $2p$ core levels show asymmetric single peak metal-like spectra, while the Mn $2p$ core levels show asymmetric doublet peaks. The relative intensities of the Mn $2p$ doublets as a function of $x$ indicate occupancy changes of distinct crystallographic sites associated with Mn up-spin and down-spin states. The valence band spectra identify the Gd $4f$ states at high binding energies ($\ensuremath{\sim}7.4$ eV). The Mn $3d$ states occur at the Fermi level and as a broad feature between 2 and 5 eV binding energy in ${\mathrm{Gd}}₆{\mathrm{Mn}}₂₃$. Upon substitution, the Fe $3d$ states show up as small shifts to higher binding energies compared to Mn $3d$ states. The Fe $3s$ and Mn $3s$ spectra show exchange split peaks, allowing an estimate of the Mn and Fe magnetic moments using a Van Vleck analysis, which also provides a quantification of occupancy changes with $x$. The overall results are consistent with the bulk net magnetization, indicating that Mn up-spin sites become Fe down-spin sites on substitution, while the nonmonotonic ${T}_C$ originates in a change from Mn sublattice to Fe sublattice derived ordering.