Relativistic Effects and the Chemistry of the Heavier Main Group Elements

Taming the Electronic Structure of Lead and Eka-lead (Flerovium) by the Relativistic Coupled Cluster Method

“…Information emerged from the present investigation using state-of-the-art theoretical calculations might be contribute to a better understanding of the theory of nuclear shell structure of SHEs, which underlies predictions of an “Island of Stability”. Present in combination with previous , studies indicated that the heaviest elements are basically homologues of their lighter congeners in the chemical groups, though their properties may be rather different due to very large relativistic effects. This is also a reason why trends in atomic (and molecular) properties may change in going over to the heaviest elements.…”

“…The study of the superheavy elements (SHE) having atomic numbers greater than 100 has gained tremendous impetus during the last few decades owing to the motivation obtained from the search for the “island of stability”, culminating in the extension of the modern form of the periodic table. , Significant progress has been made in recent years in creating new SHEs. − After the synthesis of elements 110–112 in 1994–96, − elements 114 and 116 were reported in 1999 , and 2000 . The latter atoms are a subject of great interest, as they fall within the “island of stability” predicted by nuclear physics.…”

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M2 (M = Cu, Ag, Au, Rg)

“…For relativistic effect in chemistry, Dirac stated that it would be of little use in the consideration of molecular structures or ordinary chemical reactions in 1929, and chemists by and large agreed with his assertion until the 1970s. , Nevertheless, the relativistic effects turn out to be noticeable in all the elements and are significant for the ground states of molecules roughly beginning from the elements in the sixth row (Cs–Rn), especially for lanthanides, actinides, and the superheavy elements of the period table. − For example, the so-called 6s 2 inert pair effect refers to a tendency for this pair of 6s 2 electrons to resist oxidation due to the stabilization resulting from the dominating direct relativistic effects . − Related to relativistic effects, many unexpected and novel properties are brought into the chemistry of the heavier elements with high atomic numbers, − gold and mercury being prominent examples of such. ,− Superheavy elements have especially significant relativistic effects. These elements can be studied by means of the gas-phase chromatography technique due to their strong volatilities, whereby they are deposited on the detector surfaces.…”

Pressure-Stabilized Ir3– in a Superconducting Potassium Iridide

“…Late 5d transition metals, such as Pt, Au, and Hg, exhibit some of the most distinctive crystal chemistry on the periodic table because their propensity to both oxidize, becoming cationic, and reduce, becoming anionic. 1,2 The ability to gain electrons stems from a combination of relativistic effects and the lanthanide contraction, which causes a massive effective nuclear charge on the valence electrons. 3−5 Consequently, these metals have unusually high electron affinities; in fact, the electron affinities of Pt and Au are 2.13 and 2.30 eV, respectively, which are both greater than those of many main group elements including sulfur (2.08 eV).…”

“…Late 5d transition metals, such as Pt, Au, and Hg, exhibit some of the most distinctive crystal chemistry on the periodic table because their propensity to both oxidize, becoming cationic, and reduce, becoming anionic. , The ability to gain electrons stems from a combination of relativistic effects and the lanthanide contraction, which causes a massive effective nuclear charge on the valence electrons. − Consequently, these metals have unusually high electron affinities; in fact, the electron affinities of Pt and Au are 2.13 and 2.30 eV, respectively, which are both greater than those of many main group elements including sulfur (2.08 eV). , The most notable compound with an anionic transition metal is cesium auride, CsAu, which adopts the CsCl-type crystal structure . Although the assignment of formal charges in extended solids is often ambiguous, a combination of 197 Au Mössbauer spectroscopic analysis, electrochemical studies, , and computational modeling provides definitive support for the presence of Au – .…”