title: An 18-electron system containing a superheavy element: theoretical studies of sg@au12.
abstract: M@Au12 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@Au12 cluster is also stable. Geometric and electronic structures and bonding of various Sg@Au12 isomers were investigated with density functional theory (PW91, PBE, B3LYP) and wave function theory (MP2, CCSD(T)) approaches. The lowest-energy isomer of Sg@Au12 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 Au12 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 ∼0.8 eV of bond energy per each of the 12 Sg-Au 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@Au12 than for Sg@Au12 or Au@Au12.
authors: †Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.|§Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering, Ministry of Education, Tsinghua University, Beijing 100084, China.
authors: Guo-Jin
authors: GJ
authors: Cao
authors: §Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering, Ministry of Education, Tsinghua University, Beijing 100084, China.|∥Physical and Theoretical Chemistry, University of Siegen, Siegen 57068, Germany.
authors: W H Eugen
authors: WH
authors: Schwarz
authors: §Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering, Ministry of Education, Tsinghua University, Beijing 100084, China.
authors: Jun
authors: J
authors: Li