Study on structures, stabilities, electronic and magnetic properties of zirconium-doped magnesium clusters Zr ₂ Mg n

Transition metal zirconium-doped magnesium clusters, Zr2Mgn (n = 1–11), were studied through a collaborative combination of the CALYPSO code and DFT calculations. The results show that the Zr2Mgn clusters have a structural transition from 2D to 3D at n = 2. The octahedral and pentagonal bipyramidal structures act as the basic units of subsequent structures to produce many derivative clusters from n = 6. In all Zr2Mgn clusters, Zr atoms tend to occupy high coordination positions and bind to most Mg atoms. Charge analysis reveals an electron transfer from Mg to Zr and significant spd hybridization behaviour in Zr2Mgn. Stability calculation suggests that the pentagonal bipyramid Zr2Mg5 cluster has a prominent stability, which benefits from its closed-shell electronic structure. The subsequent bonding analysis indicates that the bond order is Zr-Zr > Zr-Mg > Mg-Mg in the Zr2Mg5 cluster. For most sizes of Zr2Mgn, doping of Zr atoms induces a certain amount of magnetic moments, where the Zr2Mg, Zr2Mg7, and Zr2Mg8 clusters all have the largest magnetic moment of 4 μB.