Photoelectron Imaging Signature for Selective Formation of Icosahedral Anionic Silver Cages Encapsulating Group 5 Elements: M@Ag12− (M = V, Nb, and Ta)

20 February 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


An assembly of thirteen atoms can build up highly symmetric architectures like those belonging to D3h, Oh, D5h, and Ih point groups. However, an intuitive experimental signature that reveals their structural symmetries has been difficult to obtain. Here, using photoelectron imaging spectroscopy in combination with density functional theory calculations, we present simple yet convincing evidence for selective formation of icosahedral cages in anionic silver clusters encapsulating a dopant atom of group 5 elements: M@Ag12− (M = V, Nb, and Ta). Their photoelectron images obtained at 4 eV closely resemble one another: only a single ring is observed, which is assignable to photodetachment signals from a five-fold degenerate superatomic 1D electronic shell in the 1S21P61D10 configuration of valence electrons. The perfect degeneracy of the 1D orbital represents an unambiguous fingerprint of an icosahedral symmetry, which would otherwise be lifted in all the other possible structural isomers.


Structural determination
Geometric isomer selectivity
Metal clusters
Group theory
Photoelectron imaging

Supplementary materials

Supporting Information
Supporting information presenting the experimental methods and several computational results regarding the main text.


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