Abstract: The structural stabilities and crystal evolution behaviors of the hyper stoichiometric compound ZrC₂ (carbon rich; C/Zr > 1.0) are studied under ambient and high pressure conditions using first-principles calculations in combination with the particle-swarm optimization algorithm. Six viable structures of ZrC₂ in P2₁/c, Cmmm, Cmc2₁, P4₂/nmc, Immm and P6/mmm symmetries are identified. These structures are dynamically stable as their phonon spectra have no imaginary modes at zero pressure or at the selected high-pressure points. Among them, the P2₁/c phase represents the ground state structure, whereas P2₁/c, P4₂/nmc, Immm and P6/mmm phases are part of the phase transition series. The phase order and critical pressures of the phase transition are determined to be approximately 300 GPa according to the equation of states and enthalpy. Furthermore, the mechanical and electronic properties are investigated. The P2₁/c and Cmc2₁ phases display a semi-metal nature, whereas the P4₂/nmc, Immm, P6/mmm and Cmmm phases exhibit a metallic nature. Moreover, the present study reveals considerable information regarding the structural, mechanical and electronic properties of ZrC₂, thereby providing key insights into its material properties and evaluating its behavior in practical applications.

Key words: crystal structure, phase transition, mechanical property, electronic band, first-principles calculation