Relativistic Effects and the Chemistry of the Heaviest Main-Group Elements

Abstract

The heaviest main-group elements (mercury through radon and their heavier congenors) often show markedly different chemical properties than their lighter counterparts. Most of these differences arise from changes in the relative energies of the outer-shell atomic orbitals that can be explained by application of Einstein's theory of special relativity ("relativistic effects") to electrons in atoms. Changes include stabilization of lower oxidation states, destabilization of higher states, and greater tendencies towards cluster formation. These will be illustrated by examples of recent research reports, and predictions for the chemistry of elements 112 through 118.

Directionality of Pb2+ lone pair electrons dictated hemi‐directed coordination mode of methyl‐ and ferrocenylcarboxylate complexes

“…At the same time, it necessitates to account the relativistic effects in the electronic structure calculations of Pb 2+ complexes. Hence, the treatment of relativistic effects for heavy elements has been considered by relativistic effective core potential (RECP) methods . So, we have used the relativistic quantum chemical methods for investigating the structure and coordination mode of Pb 2+ containing substituted methylcarboxylate and ferrocenylcarboxylate systems.…”

The Chemistry of Arsenic, Antimony and Bismuth

“…Accordingly, the energies of all of the ns orbitals in bismuth are substantially lower than those of arsenic and antimony. The p-orbital energies are also lower but the difference is smaller than that of the s-orbitals [29]. The lower energy of the valence 6s orbital implies that the 6s 2 lone pair of electrons is less readily available for bonding, making bismuth(III) a significantly weaker Lewis base than the lighter pnictogens and disfavouring the þ5 oxidation state for bismuth.…”

Theoretical study of the stability and properties of magic numbers (m = 5, n = 2) and (m = 6, n = 3) of bimetallic bismuth‐copper nanoclusters; Bim Cun

“…In recent years, bismuth has been the focus of research because its properties differ significantly from other members of the group 15 . The relativistic behavior of its electrons results in an inert pair effect, which stabilizes bismuth's inner electron shells, so that only p orbitals are available to interact with other species . Ion trapped electron diffraction studies carried out on synthesized cations in gas phase and density functional theory (DFT) studies on neutral clusters, indicate that small, pure bismuth nanoclusters tend to form boxes with pentagonal faces.…”