Probing the magnetic and structural properties of the 3d, 4d, 5d impurities encapsulated in an icosahedral Ag12 cage

The geometries, electronic, and magnetic properties of the 3d, 4d, 5d impurities encapsulated in an icosahedral Ag12 cage have been systematically investigated by using relativistic all-electron density functional theory with generalized gradient approximation. The general features of the properties of 3d, 4d, 5d transition-metal atoms doped Ag12 clusters are probed and compared. It is found that the most stable structure for all M@Ag12 clusters (M=3d, 4d and 5d transition-metal atoms) is the icosahedral structure with Ih symmetries, in which the transition-metal atom is located in the center of the Ag12 cage. All doped clusters show larger relative binding energies compared with pure icosahedral Ag13 cluster, indicating that doping by 3d, 4d, 5d transition-metal atoms could stabilize the Ag12 icosahedron and form a new binary alloy cluster. The calculation of the magnetic properties demonstrates that the magnetic moments of M@Ag12 clusters vary from 0 to 4μB by doping different transition-metal atom into Ag12 icosahedron, suggesting that the transition-metal-doped Ag12 clusters could have potential utility in new nanomaterials as building blocks with tunable magnetic properties.