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Updated: Aug 27, 2025
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Magic Numbers in Octahedral Ligated Metal-Chalcogenide Superatoms
Arthur C Reber1, Turbasu Sengupta1, Dinesh Bista1
1Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284-2000, United States.
Abstract:
The attainment of the superatomic state offers a unifying framework for the periodic classification of atomic clusters. Metallic clusters attain the superatomic state via the confined nearly free electron gas model that leads to groupings of quantum states marked by radial and angular momentum quantum numbers. We examine ligated octahedral metal-chalcogenide clusters where the nearly free electron gas model is invalid; however, the high symmetry can also lead to the bunching of electronic states. For octahedral TM6E8L6 clusters (TM = transition metal; E = chalcogen; L = ligand), the electronic shells are filled for valence electron counts of 96, 100, and 114 electrons. These magic electron counts are marked by large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, high ionization energies, and low electron affinity─all classic signatures of the superatomic state. We also find that clusters with electron counts differing from the magic counts show periodic patterns reminiscent of those observed in the periodic table of elements.
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