Special stability of cationic MPb12+ clusters and superalkali character of neutral MPb12 clusters (M = B, Al, Ga, In, and Tl).

The electronic structures and stabilities of cationic MPb12+ clusters (M = B, Al, Ga, In, and Tl) with 50 valence electrons are investigated within density functional theory. It is shown that, at the B3LYP/cc-pVDZ(-PP) and BPW91/cc-pVDZ(-PP) levels of theory, the structures of MPb12+ with icosahedra (I(h)) symmetry are energetically favorable, and their high stabilities may arise from the closed-shell nature of the pi subsystems which are subject to the 2(N(pi + 1)2 rule with N(pi = 1). In addition, the possessing of large nucleus-independent chemical shifts of the five kinds of clusters reflects the common aromatic character of these clusters. From the comparison of our studies on the binding energies and the highest occupied molecular orbital and the lowest unoccupied molecular orbital energy gaps, the cluster AlPb12+ has higher stability than the others and this is consistent with the recent mass-spectrometric discovery of Al-doped Pb(n)+ clusters, in which AlPb12+ is highly abundant. The same methods are used to search for the structures of the neutral MPb12 clusters. The calculations reveal that the most stable geometries of the BPb12 and GaPb12 clusters have I(h) symmetry, the AlPb12 and InPb12 clusters have T(h) symmetry, and the TlPb12 cluster has C5v symmetry. Furthermore, the vertical ionization potentials of the neutral MPb12 clusters are smaller than that of some alkali atoms, indicating that the neutral MPb12 clusters possess superalkali character.