Theoretical prediction of the configurations, electronic and magnetic properties of the transition-metal@Zn12S12 clusters

Transition-metal (TM) can adjust the magnetic properties of ZnS materials which are helpful to design novel tunable magnetic materials. The configurations, electronic and magnetic properties of the TM@Zn12S12 clusters have been investigated by using first-principles at PBE level. The results exhibit that the Sc, V, Fe, Ni, Zn, Nb, Rh, Ta and Pt atoms prefer to interact with the Zn12S12 cages by binding energy. TM atom encapsulating will greatly increase the chemical activity of the Zn12S12 clusters by the HOMO-LUMO gap. The maximum values (0.331 vertical bar e vertical bar, 1.032 vertical bar e vertical bar and 0.436 vertical bar e vertical bar) of the Milliken charges occur at Sc, Y and Lu, the minimum values (-0.111 vertical bar e vertical bar,-0.301 vertical bar e vertical bar and-0.462 vertical bar e vertical bar) of the Milliken charges occur at Cu, Rh and Pt, respectively. The maximum spins (5.484 mu B, 5.039 mu B, 1.565 mu B and 4.201 mu B) of TM atoms for the TM@Zn12S12 clusters appear as Cr, Mo, Ru and Re encapsulated.