Lattice vibrations in high-pressure phases of LiYF$_{4}$

TL;DR

This study investigates the lattice vibrations and phase stability of LiYF₄ under high pressure using lattice dynamics and molecular dynamics, revealing anomalous thermal expansion and phase transition behaviors.

Contribution

It combines lattice dynamics and molecular dynamics to analyze high-pressure phases of LiYF₄, providing new insights into their vibrational properties and phase transition mechanisms.

Findings

Predicted anomalous thermal expansion at low temperatures in phases I and IIa.

Observed irreversibility of phase II to phase III transition upon pressure release.

Provided qualitative insights into temperature-driven phase transitions and kinetic effects.

Abstract

Possible variations in the dynamical behaviour of LiYF$_{4}$ due to its several structural changes under pressure are examined by making use of the complementary techniques of quasi-harmonic lattice dynamics and molecular dynamics simulations. The phonon spectra in the entire Brillouin zone together with the respective Gibbs free energies are calculated for the three high-pressure polymorphs of LiYF$_{4}$ (that are stable at T = 0) with a view to better understand their relative stabilities as functions of pressure and temperature. The present work predicts anomalous thermal expansion at low temperatures in phases I and IIa while irreversibilty of phase II $\to$ phase III transition on subsequent pressure release. Molecular dynamics simulations provide qualitative impressions about a temperature-driven second-order transition and also of kinetic effects in the subsequent pressure-driven first-order phase transformation.