First-principles study of martensitic phase transformation of TiRh alloy

Geometric structures and atomic positions were studied with plane wave pseudo-potential method based on density functional theory for cubic, tetragonal, and monoclinic phases of TiRh alloy. Their phonon dispersion curves were obtained with frozen phonon method at harmonic approximation using density-functional perturbation theory. Our calculations revealed that both B2 and L10L10 phases are thermodynamically unstable. Jahn–Teller effect triggers the occurrence of Bain transformation from cubic to tetragonal phase, and then soft-mode phonon further leads to the transition from tetragonal to monoclinic phase on cooling. The monoclinic phase was predicted to be P2/m space group through atomic vibrational movement along [001] direction of virtual frequency modes of L10L10 phase. The temperature from B2 to L10L10 and then to P2/m were predicted to be about T=1100.53 K and T=324.48 K through free energy calculations with the electronic plus vibrational energy of formation, respectively, which is in good agreement with experimental observations.