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 density-functional, first-principles calculations. We examine the transformation of tetragonal C11b 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.