Crystal structure, Chemical Bonding, and Magnetism of α-Fe6Ga5: How Local Interactions Shape the Structure and Properties of Intermetallic Compounds.

Abstract

α-Fe6Ga5 was synthesized from the elements as a polycrystalline powder. Its crystal structure was redetermined by high-resolution powder X-ray diffraction, which showed a complex monoclinic structure of the Fe6Ge5 type. The determined lattice parameters (a = 10.08380(6) Å, b = 7.97071(5) Å, c = 7.70489(5) Å, and β = 108.3062(2)°) differ notably from the previous reports. Despite possessing the same structure type as Fe6Ge5, α-Fe6Ga5 displays several distinctive features, such as short Ga-Ga bonds and distorted Fe layers. According to magnetization measurements, α-Fe6Ga5 is a soft ferromagnet with a high Curie temperature of 760 K, which is in stark contrast to the antiferromagnetic behavior of Fe6Ge5 reported in the literature. The electronic structure of α-Fe6Ga5 was studied theoretically using density functional theory-calculations, which showed the pronouncedly covalent character of the short Fe-Ga and Ga-Ga bonds. Similar calculations were performed for Fe6Ge5, which revealed stronger Fe-Ge interactions, which preclude the formation of short Ge-Ge bonds. In both cases, the theoretical calculations showed ferromagnetic instability, which leads to ferromagnetic ordering only in the case of α-Fe6Ga5, likely due to the different nature of Fe-Ga-Fe and Fe-Ge-Fe superexchange interactions.