First-Order Phase Transition in BaNi2Ge2 and the Influence of the Valence Electron Count on Distortion of the ThCr2Si2 Structure Type

Structural instability has a strong influence on the understanding of superconductivity in iron-containing 122 phases. Similar to the 122 iron-based high-temperature superconductors, the intermetallic compound BaNi2Ge2 undergoes an orthorhombic-to-tetragonal structural phase transition. The compound was prepared by arc-melting mixtures of the elements under an argon atmosphere. Single crystals were obtained by a special heat treatment in a welded tantalum ampule. The crystal structure of the compound was investigated by powder and single-crystal X-ray diffraction. Differential thermal analysis of BaNi2Ge2 showed a reversible phase transition at ca. 480 degrees C. In situ temperature-dependent synchrotron powder X-ray diffraction studies revealed that below 480 degrees C the crystal structure of BaNi2Ge2 is orthorhombic [own structure type, space group Pnma, a = 8.3852(4) angstrom, b = 11.3174(8) angstrom, and c = 4.2902(9) angstrom at 30 degrees C] and the high-temperature phase above 510 degrees C belongs to the tetragonal ThCr2Si2-type structure [space group I4/mmm, a = 4.2664(1) angstrom, and c = 11.2537(3) angstrom at 510 degrees C]. The reversible first-order low-temperature <-> high-temperature phase transition around 480 degrees C is associated with distortion of the [Ni2Ge2] layer of low-temperature modification. The anisotropy of thermal expansion of the unit cell in BaNi2Ge2 was analyzed. The crystal chemistry and chemical bonding are discussed in terms of linear muffin-tin orbital band structure calculations and a topological analysis using the electron localization function. In related compounds, the level of distortion of the uncollapsed tetragonal ThCr2Si2-type structure depends on the valence electron count (VEC).