Anharmonicity and scissoring modes in the negative thermal expansion materials ScF$_3$ and CaZrF$_6$

TL;DR

This study investigates the mechanisms behind negative thermal expansion in ScF$_3$ and CaZrF$_6$, highlighting the role of dynamic scissoring modes and anharmonic coupling in their structural flexibility.

Contribution

It introduces a symmetry-motivated analysis of local and average structures, revealing how mode flexibility and anharmonic interactions drive NTE in these materials.

Findings

Greater dynamic distortions in CaZrF$_6$ correlate with larger NTE.

Rock-salt ordering enhances mode flexibility in CaZrF$_6$.

Anharmonic coupling contributes to high NTE in ScF$_3$.

Abstract

We use a symmetry-motivated approach to analysing X-ray pair distribution functions to study the mechanism of negative thermal expansion in two ReO$_3$-like compounds; ScF$_3$ and CaZrF$_6$. Both average and local structure suggest that it is the flexibility of M-F-M linkages (M = Ca, Zr, Sc) due to dynamic rigid and semi-rigid "scissoring" modes that facilitates the observed NTE behaviour. The amplitudes of these dynamic distortions are greater for CaZrF$_6$ than for ScF$_3$, which corresponds well with the larger magnitude of the thermal expansion reported in the literature for the former. We show that this flexbility is enhanced in CaZrF$_6$ due to the rock-salt ordering mixing the characters of two of these scissoring modes. Additionally, we show that in ScF$_3$ anharmonic coupling between the modes responsible for the structural flexibility and the rigid unit modes contributes to the unusually high NTE behaviour in this material.