Negative Thermal Expansion in cubic ZrW2O8: Role of Phonons in Entire Brillouin Zone From ab-inito Calculations

TL;DR

This study uses ab-initio calculations to analyze phonons across the entire Brillouin zone in cubic ZrW2O8, revealing specific anharmonic phonons responsible for its large negative thermal expansion and clarifying their pressure and temperature dependence.

Contribution

It provides a detailed first-principles analysis of phonons responsible for NTE in ZrW2O8, distinguishing phonons affected by pressure from those affected by temperature.

Findings

Phonons with pressure-dependent anharmonicity are linked to NTE.

Low-frequency phonon softening and hardening trends are reproduced.

Different phonons show anharmonicity with pressure versus temperature.

Abstract

We report ab-inito density functional theory calculation of phonons in cubic phase of ZrW2O8 in the entire Brillouin zone and identify specific anharmonic phonons that are responsible for large negative thermal expansion (NTE) in terms of translation, rotation and distortion of WO4 and ZrO6. We have used density functional calculations to interpret the experimental phonon spectra as a function of pressure and temperature as reported in literature. We discover that the phonons showing anharmonicty with temperature are different from those showing anharmonicity with pressure although both are of similar frequencies. Only the latter phonons are associated with NTE. Therefore the cubic and/or quadratic anharmonicity of phonons is not relevant to NTE but just the volume dependence of frequencies. The calculations are able to reproduce the observed anomalous trends, namely, the softening of the low frequency peak at about 5 meV in the phonon spectra with pressure and its hardening with temperature, while both the changes involve a compression of the lattice.