A joint experimental and theoretical study on structural, electronic, and magnetic properties of MnGe_n ^- (n = 3-14)...

A systematic structure and property investigation of MnGe_n ^- (n = 3-14) was conducted by means of density functional theory coupled with mass-selected anion photoelectron spectroscopy. This combined theoretical and experimental study allows global minimum and coexistence structures to be identified. It is found that the pentagonal bipyramid shape is the basic framework for the nascent growth process of MnGe_n ^- (n = 3-10), and from n = 10, the endohedral structures can be found. For n = 12, the anion MnGe₁₂ ^- cluster probably includes two isomers: a major isomer with a puckered hexagonal prism geometry and a minor isomer with a distorted icosahedron geometry. Specifically, the puckered hexagonal prism isomer follows the Wade-Mingos rules and can be suggested as a new kind of superatom with the magnetic property. Furthermore, the results of adaptive natural density partitioning and deformation density analyses suggest a polar covalent interaction between Ge and Mn for endohedral clusters of MnGe₁₂ ^-. The spin density and natural population analysis indicate that MnGe_n ^- clusters have high magnetic moments localized on Mn. The density of states diagram visually shows the significant spin polarization for endohedral structures and reveals the weak interaction between the Ge 4p orbital and the 4s, 3d orbitals of Mn.