An 18-Electron System Containing a Superheavy Element: Theoretical Studies of Sg@Au-12

作者：Cao Guo Jin; Schwarz W H Eugen; Li Jun^*

来源：Inorganic Chemistry, 2015, 54(7): 3695-3701.

DOI：10.1021/acs.inorgchem.5b00356

M@Au-12 cage molecules (M = transition element from group 6) are interesting clusters with high-symmetric structure and significant stability. As the heavier homologue of W is (106)Sg, it is interesting to pinpoint whether the Sg@Au-12 cluster is also stable. Geometric and electronic structures and bonding of various Sg@Au-12 isomers were investigated with density functional theory (PW91, PBE, B3LYP) and wave function theory (MP2, CCSD(T)) approaches. The lowest-energy isomer of Sg@Au-12 has icosahedral symmetry with significant Sg(6d)-Au(6s) covalent-metallic interaction and is comparable to the lighter homologues (M = Mo, W), with similar binding energy, although Sg follows (as a rare case) the textbook rule ns below (n - 1)d. The 12 6s valence electrons from Au-12 and the six 7s6d ones from Sg can be viewed as an 18e system below and above the interacting Au 5d band, forming nine delocalized multicenter bond pairs with a high stability of similar to 0.8 eV of bond energy per each of the 12 SgAu contacts. Different prescriptions (orbital, multipole-deformation, charge-partition, and X-ray-spectroscopy based ones) assign ambiguous atomic charges to the centric and peripheral atoms; atomic core-level energy shifts correspond to some negative charge shift to the gold periphery, more so for Cr@Au-12 than for Sg@Au-12 or Au@Au-12.

• 出版日期2015-4-6
• 单位山西大学; 清华大学