Design of Three-shell Icosahedral Matryoshka Clusters A@B12@A20 (A = Sn, Pb; B = Mg, Zn, Cd, Mn)

Abstract

We propose a series of icosahedral matryoshka clusters of A@B12@A20 (A = Sn, Pb; B = Mg, Zn, Cd), which possess large HOMO-LUMO gaps (1.29 to 1.54 eV) and low formation energies (0.06 to 0.21 eV/atom). A global minimum search using a genetic algorithm and density functional theory calculations confirms that such onion-like three-shell structures are the ground states for these A21B12 binary clusters. All of these icosahedral matryoshka clusters, including two previously found ones, i.e., [As@Ni12@As20]3− and [Sn@Cu12@Sn20]12−, follow the 108-electron rule, which originates from the high Ih symmetry and consequently the splitting of superatom orbitals of high angular momentum. More interestingly, two magnetic matryoshka clusters, i.e., Sn@Mn12@Sn20 and Pb@Mn12@Pb20, are designed, which combine a large magnetic moment of 28 µB, a moderate HOMO-LUMO gap, and weak inter-cluster interaction energy, making them ideal building blocks in novel magnetic materials and devices.

The Capping Theory of Chemical Clusters Based on 12N/14N Series

“…The details can only be elucidated by x-ray crystal structural analysis. In this case, the cluster of 13 skeletal elements is found to comprise of Sn at the center of an icosahedral cluster enclosed in another cluster of 20 Sn skeletal elements (Huang, et al, 2014).…”

Comprehensive genetic algorithm forab initioglobal optimisation of clusters

“…onionlike icosahedral 'matryoshka' cluster, can be also confirmed by our CGA-DFT calculations. [77] Zn 12 , have been confirmed to adopt onion-like icosahedral 'matryoshka' structure as their ground state (see Figure 9). The high stability of these 'matryoshka' clusters is then attributed to on substrate, ligand-protected metal clusters, one-dimensional nanowires and so on.…”

Inside out Capping Clusters: Matryoshka Series

“…The presence of the Magic Number 108 (Fehlner & Halet, 2007) The magic number is also present. However, the presence of108 magic number was attributed to existence of I h symmetry in the cluster (Huang, et al, 2014). In matryoshka clusters, it can be seen that the skeletal elements which are supposed to be the nucleus [m20] are actually in the outside layer and the 13 capping elements have taken the place of the nucleus.…”

“…Matryoshka clusters have attracted great attention of scientists since the beginning of this century (Moses,et al,2003;King&Zhao,2006;Stegmaier&Fä ssler,2011) due to their unique structure and bonding challenges. The extension of the research work on Zintl ions (Esenturk, et al, 2006) resulted in the discovery of Matryoshka clusters which were also described as superatoms requiring special bonding treatment (Huang, et al, 2014). The recent discovery of the simple 4N series method which was found useful in categorizing clusters such as boranes, transition metal carbonyls and metalloboranes was successfully applied to the analysis and categorization of Zintl ions (Kiremire, 2016a).…”