Author(s) Gilmour, J.T.A.; Gaston, N.
Journal Phys Chem Chem Phys
Date Published 2020 Feb 21

The geometries and electronic structures of icosahedral A (A = Sc, Y; C = 0, ±1, ±2) clusters have been determined at a range of multiplicities at each cluster charge, using density functional theory methods. These clusters demonstrate a complex electronic structure which provides insight into the anomalously high magnetic moment of icosahedral group 3 clusters and further contextualises the role of transition metals and d-electrons within the superatomic model. Embedded deeply within the density of states for these clusters are typical superatom orbitals which are populated up to the 2S level. Above the 2S-state there are three states of apparent F symmetry, which are preferentially singly occupied, followed by an abundance of approximately degenerate P-, G-, D- and F-states at the Fermi energy, which are at most singly occupied. In spite of apparent angular symmetry and a nodal structure reminiscent of superatomic orbitals these states are actually formed from preferential overlap of the valence d-orbitals of the cluster atoms. This analysis was further contextualised through analysis of the Sc cluster, which shows a similar construction of Kohn-Sham states, but with the breaking of 5-fold symmetry along one of its Cartesian axes. Finally, this work clearly demonstrates the ability of d-electrons to give rise to superatomic orbitals is not just constrained by atomic species but also by the local environment of the atoms.

DOI 10.1039/c9cp05933d
ISSN 1463-9084
Citation Phys Chem Chem Phys. 2020;22(7):40514058.