Original scientific paper

Comparison of Gold Bonding with Mercury Bonding

Elfi Kraka ; Department of Chemistry, University of the Pacific, 3601 Pacific Avenue, Stockton, CA 95211, USA
Michael Filatov ; Department of Chemistry, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747AG Groningen, Netherlands
Dieter Cremer ; Department of Chemistry, University of the Pacific, 3601 Pacific Avenue, Stockton, CA 95211, USA

Abstract

Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX+ analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energies (BDEs), bond lengths, dipole moments, and charge distributions. Relativistic effects are substantially larger for AuX than HgX molecules. AuX bonding has been contrasted with HgX bonding considering the effects of relativity, charge transfer and ionic bonding, 3-electron versus 2-electron bonding, residual π-bonding, lone pair repulsion, and the d-block effect. The interplay of the various electronic effects leads to strongly differing trends in calculated BDEs, which can be rationalized with a simple MO model based on electronegativity differences, atomic orbital energies, and their change due to scalar relativity. A relativistic increase or decrease in the BDE is directly related to relativistic changes in the 6s orbital energy and electron density.

Keywords

NESC/B3LYP; bonding theory; relativistic effects; gold halides; gold chalcogenides

Hrčak ID:

38657

URI

https://hrcak.srce.hr/38657

Publication date:

30.6.2009.

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