Effect of Atomic Mass Contrast on Lattice Thermal Conductivity: A Case Study for Alkali Halides and Alkaline-Earth Chalcogenides

Lattice thermal conductivity (κ L ) is of great scientific interest for the development of efficient energy conversion technologies. Therefore, microscopic understanding of phonon transport is critically important for designing functional materials. In our previous study (Roshan et al., ACS Applied Energy Mater. 2021, 5, 882–896), anomalous κ L trends were predicted for rocksalt alkaline-earth chalcogenides (AECs). In the present work, we extended it to alkali halides (AHs) and conducted a thorough investigation to explore the role of atomic mass contrast on lattice dynamics and phonon transport properties of 36 binary compounds (20 AHs + 16 AECs). The calculated spectral and cumulative κ L reveal that low-lying optical phonon modes significantly boost κ L alongside acoustic phonons in materials where the atomic mass ratio approaches unity and cophonocity nears zero. Phonon scattering rates are relatively low for materials with a mass ratio close to one, and the corresponding phonon lifetimes are higher, which enhances κ L . Phonon lifetimes play a critical role, outweighing phonon group velocities, in determining the anomalous trends in κ L for both AHs and AECs. To further explore the role of atomic mass contrast in κ L, the effect of tensile lattice strain on phonon transport has also been investigated. Under tensile strain, both group velocities and phonon lifetimes decrease in the low frequency range, leading to a decrease in κ L . This work provides insights on how atomic mass contrast can tune the contribution of optical phonons to κ L and its implications on scattering rates by either enhancing or suppressing κ L . These insights would aid in the selection of elements for designing new functional materials with and without atomic mass contrast to achieve relatively high and low κ L values, respectively.