Affordable Access

deepdyve-link deepdyve-link
Publisher Website

An 18-electron system containing a superheavy element: theoretical studies of [email protected]

Authors
Type
Published Article
Journal
Inorganic Chemistry
1520-510X
Publisher
American Chemical Society
Publication Date
Volume
54
Issue
7
Pages
3695–3701
Identifiers
DOI: 10.1021/acs.inorgchem.5b00356
PMID: 25797788
Source
Medline
License
Unknown

Abstract

[email protected] 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 [email protected] cluster is also stable. Geometric and electronic structures and bonding of various [email protected] isomers were investigated with density functional theory (PW91, PBE, B3LYP) and wave function theory (MP2, CCSD(T)) approaches. The lowest-energy isomer of [email protected] 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 [email protected] than for [email protected] or [email protected]

Statistics

Seen <100 times