Lattice vibrations in high-pressure phases of LiYF4_{4}

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.Comment: 13 page

Measurement of anharmonicity of phonons in negative thermal expansion compound Zn(CN)2 by high pressure inelastic neutron scattering

Zn(CN)2 is known to have an isotropic negative thermal expansion (NTE) coefficient (about -51 x 10-6 K-1) over 10-370 K that is twice as large as that of ZrW2O8. We have measured the pressure dependence of the phonon spectra up to 30 meV from a polycrystalline sample of Zn(CN)2 at pressures of 0, 0.3, 1.9 and 2.8 kbar at temperatures of 165 and 225 K. The measurements enabled us to estimate the energy dependence of the ratios Gamma/B (Gamma are Gruneisen parameters as a function of phonon energy Ei at ambient pressure and B is the bulk modulus), which reflect the anharmonicity of phonons. We conclude that the phonon modes of low energy below 15 meV play an important role in the understanding of the NTE behavior in Zn(CN)2 and the measured anharmonicity can quantitatively explain the NTE.Comment: 5 pages, 4 figure

Collective dynamics in crystalline polymorphs of ZnCl2_{2}: potential modelling and inelastic neutron scattering study

We report a phonon density of states measurement of $\alpha$-ZnCl$_{2}$ using the coherent inelastic neutron scattering technique and a lattice dynamical calculation in four crystalline phases of ZnCl$_{2}$ using a transferable interatomic potential. The model calculations agree reasonably well with the available experimental data on the structures, specific heat, Raman frequencies and their pressure variation in various crystalline phases. The calculated results have been able to provide a fair description of the vibrational as well as the thermodynamic properties of ZnCl$_{2}$ in all its four phases.Comment: Accepted in J. Phys.: Condens. Matte