The nature of structure and bonding between transition metal and mixed Si-Ge tetramers: A 20-electron superatom system.

Abstract

A novel superatom species with 20-electron system, Six Gey M(+) (x + y = 4; M = Nb, Ta), was properly proposed. The trigonal bipyramid structures for the studied systems were identified as the putative global minimum by means of the density functional theory calculations. The high chemical stability can be explained by the strong p-d hybridization between transition metal and mixed Si-Ge tetramers, and closed-shell valence electron configuration [1S(2) 1P(6) 2S(2) 1D(10) ]. Meanwhile, the chemical bondings between metal atom and the tetramers can be recognized by three localized two-center two-electron (2c-2e) and delocalized 3c-2e σ-bonds. For all the doped structures studied here, it was found that the π- and σ-electrons satisfy the 2(N + 1)(2) counting rule, and thus these clusters possess spherically double (π and σ) aromaticity, which is also confirmed by the negative nucleus-independent chemical shifts values. Consequently, all the calculated results provide a further understanding for structural stabilities and electronic properties of transition metal-doped semiconductor clusters. © 2016 Wiley Periodicals, Inc.