Quantum Chemical Study of X@Bi k Pb m , Bi k Pb m ∙X, X@Sb k Sn m , and Sb k Sn m ∙X Clusters

Clusters (Ih)-(Cd, Hg, Yb)@(Pb12, Sn12), (C5v)-(Ag, Au)@BiPb11, (C5v)-Ag@SbSn11, (D5d)(Ni, Pd, Pt)@Bi2Pb10, (D5d)-Pd@Sb2Sn10, (C3v)-(Pb12, Sn12)·(Pb, Sr, Ba), closo-Bi2Pb10, closo-Bi2Pb4, closo-Sb2Sn4, (Ih)-Bi20, (Ih)-Kr@Bi20, and (Ih)-Ni12Bi20 were studied by the DFT PBE0 method. Structures of (Ih)-(Pb, Sr)@(Pb12, Sn12), (Ih)-Ba@Pb12, (D5d)-(He, Ne)@Bi2Pb10, (C3v)-(Pb12, Sn12)∙Yb, (C5v)-(Pb12, Sn12)∙Hg, (Cs)-BiPb11∙(Ag, Au), (Cs)-SbSn11∙Ag, (Cs)-p-Bi2Pb10∙(Ni, Pd, Pt), and (Cs)-p-Sb2Sn10∙Pd clusters are metastable; structures of (Ih)-Ba@Sn12 and (D5d)-(Ar, Kr, Rn)@Bi2Pb10 are unstable. In the (Ih)-Ni12Bi20 cluster, nickel atoms form η5-bonds with the faces of the Bi20 dodecahedron. In the isomers (D4h)- and (C2v)-(Bi, Sb)2(Pb, Sn)4, 6 orbitals of lone electron pairs and 8 bonding three-center orbitals with populations of 2.00 make up a linearly dependent set of 14 natural orbitals. The oxidation state ΞX is associated with the populations of orthogonal orbitals located outside the X atom.