Understanding the Structure and Stability of a Partially Disordered “Push–Pull Alloy” Ni ₂ Zn _{11– <i>x</i>} Ga _<i>x</i> (0.4 ≤ <i>x</i> ≤ 1.25)

This study identifies two new cubic γ-brass-type phases in the Ni-Zn-Ga system: (a) Ni₂Zn_11-<i>x</i>Ga_<i>x</i> (0 < <i>x</i> ≤ 0.3) exist in a narrow homogeneity range, and the compounds crystallize in a cubic crystal system with space group of <i>I</i>4̅3<i>m</i> (<i>a</i> ≈ 9 Å), (b) Ni₂Zn_11-<i>x</i>Ga_<i>x</i> (0.4 ≤ <i>x</i> ≤ 1.25) has a broader homogeneity range and the compounds in this region adopt the primitive cubic lattice with the space group <i>P</i>4̅3<i>m</i> (<i>a</i> ≈ 9 Å). The Ga insertion into Ni₂Zn₁₁ is site specific, and at the limiting composition, Ni₂Zn₉Ga_1.25, the structure is completely ordered and comprises the two distinct clusters─a 26-atom γ-brass-type cluster (Ni₄Zn₁₈Ga₄) and a 23-atom defect body-centered cubic (bcc)-type cluster (Ni₄Zn₁₈Ga₁). The stability of these compounds can be rationalized by favorable enthalpies of formation obtained from the theoretical calculations, which correlate strongly with the coexistence of specific clusters within the primitive cubic unit cell. Electronic structure calculations indicate that these phases are stabilized by the Hume-Rothery mechanism, characterized by the presence of a pseudogap at the Fermi level. The chemical bonding analysis demonstrates that the interactions between Ni-Zn and Ni-Ga are crucial to the structural stability.