Atomic site preferences and its effect on magnetic structure in the intermetallic borides M2Fe(Ru0.8T0.2)5B2 (M=Sc, Ti, Zr; T=Ru, Rh, Ir)

The site preference for a class of intermetallic borides following the general formula M2Fe(Ru0.8T0.2)5B2 (M=Sc, Ti, Zr; T=Ru, Rh, Ir), has been explored using ab initio and semi-empirical electronic structure calculations. This intermetallic boride series contains two potential sites, the Wyckoff 2c and 8j sites, for Rh or Ir to replace Ru atoms. Since the 8j site is a nearest neighbor to the magnetically active Fe atom, whereas the 2c site is a next nearest neighbor, the substitution pattern should play an important role in the magnetic structure of these compounds. The substitution preference is analyzed based on the site energy and bond energy terms, both of which arise from a tight-binding evaluation of the electronic band energy, and are known to influence the locations of atoms in extended solids. According to these calculations, the valence electron-rich Rh and Ir atoms prefer to occupy the 8j site, a result also corroborated by experimental evidence. Additionally, substitution of Rh or Ir at the 8j site results in a modification of the magnetic structure that ultimately results in larger local magnetic moment on the Fe atoms.