First-principles prediction of magnetic superatoms in 4<i>d</i>-transition-metal-doped magnesium clusters

Abstract

We theoretically predict magnetic superatoms in the 4d-transition-metal-doped Mg8 clusters using a spin-polarized density functional theory method. We demonstrate that TcMg8 is highly energetically stable in both structure and magnetic states, and identify it as a magnetic superatom with a magnetic moment as large as 5 μB. The magnetic TcMg8 with 23 valence electrons has a configuration of 1S(2)1P(6)1D(10) closed shell and 2S(1)2D(4) open shell, complying with Hund's rule similar to the single atom. We elucidate the formation mechanism of the magnetic TcMg8 superatom based on the detailed analysis of molecular orbitals, and attribute it to the large exchange interaction and moderate crystal field effect. Finally, we predict that the magnetic TcMg8 may exhibit semiconductor-like property with spin polarization characteristics.