Crystal structure, coloring problem and magnetism of Gd5−xZrxSi4

Abstract

Ternary Gd_5−xZr_xSi₄ silicides were synthesized by arc melting of the constituent elements and subsequent heat treatments. The Gd_5−xZr_xSi₄ phases adopt the orthorhombic Gd₅Si₄-type (space groupPnma) structure for x ≤ 0.25 and the tetragonal Zr₅Si₄-type (space groupP4₁2₁2) structure for x ≥ 1.0, respectively. The samples with intermediate compositions contain two phases. Single-crystal X-ray diffraction reveals a preferential site occupancy for Zr on the three metal sites in the order of M3 > M2 > M1. Size arguments based on the local coordination environments suggest that the larger Gd atoms preferentially occupy the larger M1 site, while the smaller Zr atoms tend to occupy the smaller metal sites, M2 and M3. Tight-binding linear-muffin-tin orbital calculations illustrate a role of the metal-silicon bonds in the metal site occupation. An increase in the valence electron concentration through the Zr substitution weakens the Si–Si interactions but enhances the metal-silicon and metal-metal interactions. The Curie temperature of Gd_5−xZr_xSi₄ decreases gradually with the increasing Zr content.