Experimental and theoretical study of electron density and structure factors in CoSb3.

We refine two low-order structure factors of the skutterudite CoSb3 using convergent beam electron diffraction. The relatively large unit cell of this material causes the disks to overlap and introduces a series of challenges in the refinement procedure. These challenges and future work-arounds are discussed. The refined structure factors F200 and F600 are compared to X-ray diffraction and density functional calculated values, the latter calculated using two different functionals. Both relaxed and experimental lattice parameters are tested to explicitly highlight the impact of the lattice geometry and atomic position on the structure factors.

Comparison of the electronic structure of a thermoelectric skutterudite before and after adding rattlers: an electron energy loss study.

Skutterudites, with rattler atoms introduced in voids in the crystal unit cell, are promising thermoelectric materials. We modify the binary skutterudite with atomic content Co(8)P(24) in the cubic crystal unit cell by adding La as rattlers in all available voids and replacing Co by Fe to maintain charge balance, resulting in La(2)Fe(8)P(24). The intention is to leave the electronic structure unaltered while decreasing the thermal conductivity due to the presence of the rattlers. We compare the electronic structure of these two compounds by studying the L-edges of P and of the transition elements Co and Fe using electron energy loss spectroscopy (EELS). Our studies of the transition metal white lines show that the 3d electron count is similar for Co and Fe in these compounds. As elemental Fe has one electron less than Co, this supports the notion that each La atom donates three electrons. The L-edges of P in these two skutterudites are quite similar, signalling only minor differences in electronic structure. This is in reasonable agreement with density functional theory (DFT) calculations, and with our multiple scattering FEFF calculations of the near edge structure. However, our experimental plasmon energies and dielectric functions deviate considerably from predictions based on DFT calculations.