Zusammenfassung
Two new series of ternary gallides with the chemical formulas (La, Ce, Pr, Nd, Sm)AuxGa4−x and (La, Ce, Pr, Nd, Sm)Au1.5Ga2.5 were synthesized from the elements by arc melting. From X-ray powder diffraction analysis the REAuxGa4−x series of compounds was found to be isotypic and crystallize with BaAl4 type of structure; the homogeneity range at 600°C of each of the REAuxGa4−x phases was established, revealing remarkable deviations from Vegard's rule. At 600°C the REAuxGa4−x phases of the BaAl4 type were observed to be in thermodynamic equilibrium with a structure variant crystallizing at the composition REAu1.5Ga2.5 and with a narrow homogeneous range. In case of PrAu1.5Ga2.5 the structure type was refined from X-ray single-crystal counter data (CaBe2Ge2 type, space group View the MathML source). Gold and gallium atoms were generally found on separate crystallographic sites; however, a statistical distribution of 51% Au + 49% Ga was derived for the 2b sites. 197Au Mössbauer spectroscopy confirmed the occupational mode of the gold atoms in CeAu1.5Ga2.5. For the BaAl4-type phases, X-ray powder and Mössbauer data revealed preferential occupation of the 4e sites of View the MathML source by gold atoms; practically no Au was observed on the 4d sites. Magnetic susceptibilities were determined over a temperature range extending from 2 to 1100 K. Above liquid nitrogen temperatures the paramagnetic behavior of the (Ce, Pr, Nd)AuxGa4−x and the (Ce, Pr, Nd)Au1.5Ga2.5 compounds is characterized by magnetic moments close to the ideal trivalent rare earth values. Lanthanum compounds are diamagnetic, whereas SmAuxGa4−x alloys are characterized by a typical Van Vleck-type paramagnetism of closely spaced multiplets. At very low temperatures onset of ferromagnetic ordering is observed for the BaAl4-type series of compounds. No superconductivity was encountered down to 2 K.
