Violation of the T −1 Relationship in the Lattice Thermal Conductivity of Mg 3 Sb 2 with Locally Asymmetric Vibrations

Most crystalline materials follow the guidelines of T −1 temperature-dependent lattice thermal conductivity ( κ L ) at elevated temperatures. Here, we observe a weak temperature dependence of κ L in Mg 3 Sb 2 , T −0.48 from theory and T −0.57 from measurements, based on a comprehensive study combining ab initio molecular dynamics calculations and experimental measurements on single crystal Mg 3 Sb 2 . These results can be understood in terms of the so-called “phonon renormalization” effects due to the strong temperature dependence of the interatomic force constants (IFCs). The increasing temperature leads to the frequency upshifting for those low-frequency phonons dominating heat transport, and more importantly, the phonon-phonon interactions are weakened. In-depth analysis reveals that the phenomenon is closely related to the temperature-induced asymmetric movements of Mg atoms within MgSb 4 tetrahedron. With increasing temperature, these Mg atoms tend to locate at the areas with relatively low force in the force profile, leading to reduced effective 3 rd -order IFCs. The locally asymmetrical atomic movements at elevated temperatures can be further treated as an indicator of temperature-induced variations of IFCs and thus relatively strong phonon renormalization. The present work sheds light on the fundamental origins of anomalous temperature dependence of κ L in thermoelectrics.