On Chemical Bonding in ht-Ga3Rh and Its Effect on Structural Organization and Thermoelectric Behavior

In the course of systematic studies of intermetallic compounds Ga3TM (TMtransition metal), the compound Ga3Rh is synthesized by direct reaction of the elements at 700 °C. The material obtained is characterized as a high-temperature modification of Ga3Rh. Powder and single-crystal X-ray diffraction analyses reveal tetragonal symmetry (space group P42/mnm, No. 146) with a = 6.4808(2) Å and c = 6.5267(2) Å. Large values and strong anisotropy of the atomic displacement parameters of Ga atoms indicate essential disorder in the crystal structure. A split-position technique is applied to describe the real crystal structure of ht-Ga3Rh. Bonding analysis in ht-Ga3Rh performed on ordered models with the space groups P1̅, P42 nm, and P42212 shows, besides the omnipresent heteroatomic Ga–Rh bonds in the rhombic prisms ∞ 3[Ga8/2Rh2], the formation of homoatomic Ga–Ga bonds bridging the Rh–Rh contacts and the absence of significant Rh–Rh bonding. These features are essential reasons for the experimentally observed disorder in the lattice. In agreement with the calculated electronic density of states, ht-Ga3Rh shows temperature-dependent electrical resistivity of a “bad metal”. The very low lattice thermal conductivity of less than 0.5 W m–1 K–1 at 300 K, being lower than those for most other Ga3TM compounds, correlates with the enhanced bonding complexity.