Relativistic Effects in Gold Chemistry

Chemical and physical effects are manyfold [193]. The contraction leads to gold forming shorter and stronger covalent bonds and is likely to be 

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Schwerdtfeger, P. (1989) Relativistic effects in gold chemistry. II. The stability of complex halides of Au(III). Journal of the American Chemical Society, 111, 7261-7262. 

Schwerdtfeger, P. and Bowmaker, G.A. (1994) Relativistic effects in gold chemistry. V. Group 11 Dipole-Polarizabilities and Weak Bonding in Monocarbonyl Compounds. Journal of Chemical Physics, 100, 4487-4497. 

Wesendrup, R., Laerdahl, J.K and Schwerdtfeger, P. (1999) Relativistic Effects in Gold Chemistry. VI. Coupled Cluster Calculations for the Isoelectronic Series AuPt , Au2 and AuHg. Joumul of Chemical Physics, 110, 9457-9462. 

Schwarz, G. A. Bowmaker, P. D. W. Boyd. Relativistic effects in gold chemistry. I. Diatomic gold compounds. /. Chem. Phys., 91(1989) 1762-1774. 

Schwerdtfeger, P. (2002) Relativistic Effects in Properties of Gold. Heteroatom Chemistry, 13, 578-584. 

It was not until the 1970s that the full relevance of relativistic effects in heavy-element chemistry was discovered. However, for the sixth row (W---Bi), relativistic effects are comparable to usual shell-structure effects and therefore provide an explanation for many unusual properties of gold chemistry155-159. The main effects on atomic orbitals are (i) the relativistic radial contraction and energetic stabilization of the s and p shells, (ii) the spin-orbit splitting and (iii) the relativistic radial expansion and energetic destabilization of the outer d and f shells. 

Some central questions of the field could only be answered by computational chemistry. Often, the superior reactivity of gold was globally explained by relativistic effects, which per se is not a good argument. Platinum has 80% of the relativistic effects of gold, and thus it should show 80% of the catalytic activity. But the observed rate differences can be 1,000 and more as described in Fig. 5 of... 

The collection of these new observations has attended a revived interest in the theoretical chemistry to explain the behavior of the heaviest elements of the Periodic Table on the basis of relativistic effects, which are specially important for elements with a high nuclear charge.4-6 It is only through the consideration of the relativistic effects that a deeper understanding of the chemistry of gold has emerged.7... 

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