On the Switching between Negative and Positive Thermal Expansion in Framework Structures

TL;DR

This paper explores how adjusting the lattice parameter in framework structures can switch thermal expansion from negative to positive by altering the potential energy landscape of octahedral rotations, aiding materials design.

Contribution

It demonstrates that controlling the lattice parameter can switch thermal expansion behavior by modifying the potential energy of octahedral rotations in framework structures.

Findings

Lattice parameter influences thermal expansion behavior.

External pressure or chemical modifications can switch NTE to PTE.

Potential energy landscape determines expansion type.

Abstract

Thermal expansion is a problem in many technological applications and its control represents a challenge in materials design. In this Letter, after studying the correlation between thermal expansion, cubic-to-rhombohedral transition and lattice parameter of ReO3-type structures, I show how in the different methods for controlling thermal expansion the key element is actually the lattice parameter. By varying the lattice parameter through external pressure, chemical modifications or other methods, the single-well potential energy of the octahedral rotation, responsible for Negative Thermal Expansion (NTE), can be turned into a quartic anharmonic potential or into a double-well potential, thus enhancing or suppressing the NTE, respectively. This result can be extended to other framework-structures and should be taken into account to overcome the challenge of controlling thermal expansion.