We investigate the electronic structure of the skutterudite-related ${\mathrm{Ce}}_3{M}_4{\mathrm{Sn}}_{13}$ compounds, where metal $M$ is Co, Ru, or Rh, using x-ray photoemission spectroscopy (XPS) and band structure calculations, both within local density approximation scheme and within scheme including additional Coulomb correlations (LDA+$U$). The $d$-electron states located near the Fermi level slightly change the intensity with applying the correlation energy $U$. We note the large impact of $d$-electron correlation, which is clearly observed in the change of Ce $5p$ states located about 18 eV in the valence band. Namely, for ${\mathrm{Ce}}_3{\mathrm{Rh}}_4{\mathrm{Sn}}_{13}$ and ${\mathrm{Ce}}_3{\mathrm{Ru}}_4{\mathrm{Sn}}_{13}$ the $d$-electron correlations significantly shift the $5p$ states towards higher binding energies, while for ${\mathrm{Ce}}_3{\mathrm{Co}}_4{\mathrm{Sn}}_{13}$ the energy of the Ce $5p$ states almost does not depend on $U$. The influence of the $d$-electron correlations is also manifested by the positive magnetoresistivity (MR) of ${\mathrm{Ce}}_3{\mathrm{Rh}}_4{\mathrm{Sn}}_{13}$ and the ${\mathrm{Ce}}_{3-x}{\mathrm{La}}_x{\mathrm{Rh}}_4{\mathrm{Sn}}_{13}$ alloys that reaches 40% at the highest magnetic field ($B=9$ T) for the sample $x=0.6$, whereas only a small positive $\text{MR}\sim 0.5\%$ is observed in ${\mathrm{Ce}}_3{\mathrm{Ru}}_4{\mathrm{Sn}}_{13}$. The magnetoresistivity of ${\mathrm{Ce}}_3{\mathrm{Co}}_4{\mathrm{Sn}}_{13}$ exhibits quite different behavior and is negative.

• Received 30 September 2014
• Revised 18 December 2014

DOI:https://doi.org/10.1103/PhysRevB.91.035101