Thorium dicarbide under high pressure and high temperature: Ab initio investigation

Abstract

A systematic study on the structural stability of thorium dicarbide (ThC2) under hydrostatic compression has been carried out by exploiting the evolutionary structure search algorithm as implemented in the universal structure predictor: evolutionary Xtallography (USPEX) code in conjunction with the ab initio electronic band structure calculation method. At ambient conditions, ThC2 exists in a monoclinic crystallographic phase with space group (SG) C2/c. Our calculations under generalized gradient approximation (GGA) predict the high-pressure structural sequence of monoclinic-I (SG C2/c) → monoclinic-II (SG C2/m) → orthorhombic-I (SG Pmma) → orthorhombic-II (SG Immm) → hexagonal (SG P6/mmm) for this material with transition pressures of ∼3.3, 58.3, 191.6, and 255 GPa, respectively. Out of this theoretically predicted high-pressure structural phase transition sequence, only the first transition, i.e., monoclinic-I → monoclinic-II, could be compared with the available high-pressure experimental study by Guo et al. [Sci. Rep. 7, 45872 (2017)]. The theoretically determined phase transition qualitatively agrees with the experimental results [Y. Guo et al. Sci. Rep. 7, 45872 (2017)]. Interestingly, our predicted intermediate orthorhombic-I (SG Pmma) phase has an enthalpy lower than that of the previously predicted orthorhombic Cmmm phase by Guo et al. [Sci. Rep. 7, 45872 (2017)]. The high-pressure structural sequence so predicted through static lattice calculations has been further substantiated by confirming the elastic and lattice dynamic stability of each structure in the pressure regime of its structural stability. Additionally, the superconducting transition temperature for all these structures has been determined and it is found that the monoclinic-II (C2/m) phase has the highest transition temperature of 17 K at 5 GPa. Furthermore, the thermo-physical properties along with the temperature-induced phase transitions in ThC2 have also been investigated through both the lattice dynamic simulations (within quasi-harmonic approximation) and ab initio molecular dynamics simulations.