Design of three-shell icosahedral matryoshka clusters A@B₁₂@A2₂₀ (A = Sn, Pb; B = Mg, Zn, Cd, Mn).
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.
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Xiaoming
X
Huang
1] Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China [2] Beijing Computational Science Research Center, Beijing 100089, China.
Jijun
J
Zhao
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Yan
Y
Su
Department of Chemistry, Institute for Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00923, USA.
Zhongfang
Z
Chen
Department of Chemistry and Center for Computational Chemistry, University of Georgia, Athens, Georgia, USA.
R Bruce
RB
King