Electronic origin of negative thermal expansion in samarium hexaboride revealed by X-ray diffraction and total scattering.

Samarium hexaboride, SmB 6 , is a negative thermal expansion (NTE) material whose structure is similar to other known NTE materials such as the family of Prussian blues. In the Prussian blues, NTE is due to a phonon mechanism, but we recently showed from DFT calculations that this is unlikely in SmB 6 (Li et al. , Phys. Chem. Chem. Phys . 2023, 25 , 10749). We now report experimental X-ray diffraction and pair distribution function analysis of this material in the temperature range 20-300 K. The interatomic distances shown by both methods are consistent with the NTE instead arising from an electronic effect, by which the samarium atoms lose electrons and thus have a smaller ionic radius as the temperature increases.