First-principles study of ground-state properties and high pressure behavior of ThO2

The mechanical properties, electronic structure and phonon dispersion of ground state ThO2 as well as the structure behavior up to 240 GPa are studied using first-principles density-functional theory. Our calculated elastic constants indicate that both the ground-state fluorite structure and high pressure cotunnite structure of ThO2 are mechanically stable. The bulk modulus, shear modulus, and Young’s modulus of cotunnite ThO2 are all smaller by approximately 25% compared with those of fluorite ThO2. The Poisson’s ratios of both structures are approximately equal to 0.3 and the hardness of fluorite ThO2 is 22.4 GPa. The electronic structure and bonding nature of fluorite ThO2 are fully analyzed, and show that the Th–O bond displays a mixed ionic/covalent character. The phase transition from the fluorite to cotunnite structure is calculated to occur at the pressure of 26.5 GPa, consistent with recent experimental measurement by Idiri et al. [1]. For the cotunnite phase it is further predicted that an isostructural transition takes place in the pressure region of 80–130 GPa.