Role of filler lanthanide ions on lattice dynamics of phosphide skutterudites RFe_4P_12 (R = La, Ce, and Pr) from first principles

Phosphide skutterudites primarily show promise for thermoelectric applications due to their chemical stability at high temperatures and relatively low cost. Ion doping and band gap engineering have been used to enhance their typically poor thermoelectric performance, opening avenues for practical applications. Herein, we report a comparative lattice dynamics study on the impact of filler and temperature on the structural and vibrational properties of RFe_4P_12 (R = La, Ce, and Pr) skutterudites. Calculations are performed within the quasi-harmonic approximation, and the results are critically compared against experimental data and other ab initio calculations. We found gaps between the heat-carrying acoustic and optical modes, a-o gaps, of approximately 4, -2, and 0.01 cm^-1 for La, Ce, and Pr compounds, respectively. These results suggest a filler-induced reduction in the a-o gap is attributed to the softening of the optical modes instead of the conventionally considered upward shift of acoustic modes proposed in the rattling scenario. The distinct softening of the optical modes is rationalized by the stiffening of chemical bonds between the filler and host lattice.