Theoretical Analysis of the Mackay Icosahedral Cluster Pd55(PiPr3)12(μ3‐CO)20: An Open‐Shell 20‐Electron Superatom.

The electronic structure of the spherical Mackay icosahedral nanosized cluster Pd55(PiPr3)12(μ3‐CO)20 is analyzed by using DFT calculations. Results reveal that it can be considered as a regular superatom with a "magic" electron count of 20, characterized by a 1S2 1P6 1D10 2S2jellium configuration. Its open shell nature is associated with partial occupation of non‐jellium, 4d‐type, levels located on the interior of the Pd55 kernel. This shows that the superatom model can be used to rationalize the bonding and stability of spherical ligated group 10 clusters, despite their apparent 0‐electron count. [ABSTRACT FROM AUTHOR]