New predicted ground state and high pressure phases of TcB3 and TcB4: First-principles

Abstract The energetically favorite crystal structures at special composition for Tc-B system are studied systematically based on the density functional theory combined with the particle-swarm optimization (PSO) method. The experimentally obtained structure hP6-TcB2 is in excellent agreement with the predicted one. Moreover, a new ground state phase hP4-TcB3 (P-6m2, No. 187) is predicted for stoichiometric ratio as 1:3 (TcB3) for the first time. For TcB4, the predicted favorite hP10-TcB4 (P63/mmc, No. 194) is metastable at 0 GPa and becomes the absolutely stable phase at 100 GPa. The hP6-TcB2 exhibits the highest shear modulus of 269 GPa, and smallest Poisson’s ratio of 0.188, followed by hP10-TcB4 (239 GPa and 0.200), and then hP4-TcB3 (237 GPa and 0.209). Those are comparable to the experimental data (267 GPa and 0.15) of ReB2. The calculated convex hull and phonon dispersions indicate that all the newly predicted structures for Tc-B system are thermodynamically and dynamically stable. The computed DOS illustrates the metallic nature of considered compounds. Moreover, the high hardness about 39.4, 32.4, and 30.7 GPa are estimated to the most stable hP6-TcB2, hP10-TcB4, and hP4-TcB3, respectively, indicating these might be the candidates for hard or ultra-incompressible materials.

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