Lattice vibrations in high-pressure phases of LiYF₄

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Possible variations in the dynamical behaviour of LiYF₄ 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 LiYF₄ (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 → 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.