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.
Highlights
We propose a series of icosahedral matryoshka clusters of A@B12@A20 (A 5 Sn, Pb; B 5 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)
Using global optimization combined with density functional theory (DFT) calculations, Ferrando’s group[40] has recently achieved a series of three-shell high-symmetry matryoshka clusters, including a Ni13@Mg20 that is isostructural to the clusters considered here
A DFT-based global minimum search confirms that such icosahedral matryoshka structures are ground state configurations for these A21B12 (A 5 Sn, Pb; B 5 Mg, Zn, Cd) binary clusters
Summary
We propose a series of icosahedral matryoshka clusters of A@B12@A20 (A 5 Sn, Pb; B 5 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]32 and [Sn@ Cu12@Sn20]122, follow the 108-electron rule, which originates from the high Ih symmetry and the splitting of superatom orbitals of high angular momentum. Some specific clusters with appreciable stability mimic the chemical behavior of elemental atoms in the periodic table and can be regarded as ‘‘superatoms’’21–24 In these superatom clusters, the electronic states are delocalized over the entire cluster with spatial shapes resembling the atomic orbitals. Our results extend the scope of icosahedral matryoshka clusters and provide novel building blocks for cluster-based materials and devices exhibiting fascinating novel magnetic and optical properties
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