Isotropic Zero Thermal Expansion and Local Vibrational Dynamics in (Sc,Fe)F3

Scandium fluoride (ScF3) exhibits a pronounced negative thermal expansion (NTE), which can be suppressed and ultimately transformed into an isotropic zero thermal expansion (ZTE) by partially substituting Sc with Fe in (Sc0.8Fe0.2)F3 (Fe20). The latter displays a rather small coefficient of thermal expansion of −0.17 × 10−6/K from 300 to 700 K. Synchrotron X-ray and neutron pair distribution functions confirm that the Sc/ Fe−F bond has positive thermal expansion (PTE). Local vibrational dynamics based on extended X-ray absorption fine structure indicates a decreased anisotropy of relative vibration in the Sc/Fe−F bond. Combined analysis proposes a delicate balance between the counteracting effects of the chemical bond PTE and NTE from transverse vibration. The present study extends the scope of isotropic ZTE compounds and, more significantly, provides a complete local vibrational dynamics to shed light on the ZTE mechanism in chemically tailored NTE compounds.