First-principles calculations of phase transition, elasticity, phonon spectra, and thermodynamic properties for CeO2 polymorphs

Abstract

In this work, the structural transformation, elastic behavior, phonon spectra and thermodynamic properties of CeO2 under compressive and tensile loading were investigated by first-principles calculations based on density generalized function theory (DFT). Our calculated structural parameters and transition pressure under compressive condition are in good agreement with the experimental values. Under tensile condition, the phase transitions of CeO2 from fluorite-type (space group Fm3¯m) phase to cotunnite-type (space group Pnma), rutile-type (space group P 42/mnm) and marcasite-type (space group Pnnm) phases were predicted to occur at 23.2 ​GPa, −7.69 ​GPa, and −7.75 ​GPa respectively. The mechanical stability criteria are verified in terms of elastic constants and shows that the cotunnite and fluorite structures of CeO2 are mechanically stable in the studied pressure range, while the rutile and marcasite structures turn out to be mechanical unstable under high pressure. The calculated phonon spectra of CeO2 polymorphs demonstrate that all phases considered in present work are dynamically stable under ambient pressure. Furthermore, the calculated heat capacity, isothermal bulk modulus, Gibbs free energy, thermally expanding coefficient of CeO2 polymorphs as a function of temperature are discussed and compared with available experimental data.