DFT study of pressure induced phase transitions in LiYF4

TL;DR

This study uses density functional theory to analyze pressure-induced phase transitions in LiYF4, identifying structural changes and vibrational spectrum modifications up to 20 GPa, with findings aligning with experimental data.

Contribution

First DFT-based investigation of pressure effects on LiYF4's phase transitions, revealing structural stability and vibrational behavior under high pressure.

Findings

Transition volume agrees with experiments

Transition pressure overestimated by 6 GPa

Most stable phase at 20 GPa is P21/c structure

Abstract

An investigation of the pressure induced phase transition from the scheelite phase (I41/a, Z=4) to the fergusonite-like phase (I2/a, Z=4)/LaTaO(P21/c, Z=4) of LiYF4 is presented. Employing density functional theory (DFT) within the generalized gradient approximation, the internal degrees of freedom were relaxed for a pressure range of 0 GPa to 20 Gpa. The influence of pressure on the lattice vibration spectrum of the scheelite phase (I41/a, Z=4) was evaluated using the direct approach, i.e. using force constants calculated from atomic displacements. The transition volume is in good agreement with experiment, while the transition pressure is overestimated of 6 GPa. At 20 GPa, a P21/c structure with apentacoordinated lithium cation is found to be the most stable phase. This structure is compatible with a transition driven by a Bg zone-center soft optic mode linked to a soft-acoustic mode along the [11-1] direction as observed for the proper ferroelastic transition of BiVO4.