Indirect phase transition of TiC, ZrC, and HfC crystal structures

Abstract

AbstractWe have performed first‐principles calculations to analyze the electronic structures, static, and dynamical structural stabilities of the pressure‐induced phase transformation of refractory compounds (transition‐metal carbides) from NaCl‐type (B1) to CsCl‐type (B2) via zinc‐blende phase using the plane‐wave pseudopotential approach in the framework of the generalized gradient approximation (GGA) for the exchange and correlation functional. The ground‐state properties, equilibrium lattice constant, bulk moduli, and band structures are determined for the stoichiometry of the compounds and compared with known experimental and theoretical values. We find that the phase‐transition pressure for the indirect phase transition from B1B2 via zinc‐blende structure is about 17‐fold for TiC, 12‐fold for both ZrC and HfC, respectively, when compared with the direct phase transition. Calculated phonon instability exists for the CsCl‐B2 phase, which can prevent the structures from forming and contrary to the zinc‐blende and the NaCl‐B1 phases. The band dispersion and electronic density of states for B1 and B2 crystal phases were explored and found to indicate metallic character in contrast with the zinc‐blende phase, which has a pseudogap opening in the bandgap region suggesting a semiconducting property and also a frequency gap in the phonon spectrum.