Comparison of theoretical and experimental dielectric functions: Electron energy-loss spectroscopy and density-functional calculations on skutterudites

Abstract

We explore the possibility of combining density functional theory (DFT) and electron energy loss spectroscopy (EELS) to determine the dielectric function of materials. As model systems we use the skutterudites ${\mathrm{CoP}}_{3}$, ${\mathrm{CoAs}}_{3}$, and ${\mathrm{CoSb}}_{3}$ which are prototypes for thermoelectric materials. We achieve qualitative agreement between the theoretically and experimentally obtained low energy-loss spectra and dielectric function. Some of the remaining discrepancies may be caused by the challenge of refining the experimental spectra before Kramers-Kronig analysis. However, contrary to what is the case for some crystals with less complicated electronic structure, the DFT calculated plasmon energies deviate significantly from the experimental values. The great accuracy with which the plasmon energy can be determined by EELS, suggests that this technique may provide valuable inputs in further efforts to improve DFT calculations. The use of EELS as the experimental technique may become particularly powerful in studies of small volumes of materials.