A comparative first-principles study of martensitic phase transformations in TiPd2 and TiPd intermetallics

Martensitic phase transformations in TiPd2 and TiPd alloys are studied employing densityfunctional, first-principles calculations. We examine the transformation of tetragonal C11(b) TiPd2 to the low-temperature orthorhombic phase (C11b. oI6), and the transformation of cubic B2 TiPd under orthorhombic (B2 B19) and subsequent monoclinic transformations (B19 B19') as the system is cooled. We employ a theoretical approach based on a phenomenological Landau theory of the structural phase transitions and a mean-field approximation for the free energy, utilizing first-principles calculations to obtain the deformation energy as a function of strains and to deduce parameters for constructing the free energy. The predicted transition temperature for the TiPd2 C11b. oI6 transition is in good agreement with reported experimental results. To investigate the TiPd B2 B19 transformation, we employ both the Cauchy-Born rule and a soft-mode-based approach, and elucidate the importance of the coupling between lattice distortion and atomic displacements (i.e. shuffling) in the formation of the final structure. The calculated B2 B19 transition temperature for TiPd alloy agrees well with the experimental results. We also find that there exists a very small but finite (0.0005 eV/atom) energy barrier of B19 TiPd under monoclinic deformation for B19. B19' structural phase transformation.