The chemical bond between Au(I) and the noble gases.: Comparative study of NgAuF and NgAu+ (Ng = Ar, Kr, Xe) by density functional and coupled cluster methods

The nature of the chemical bond between gold and the noble gases in the simplest prototype of Au(I) complexes (NgAuF and NgAu(+), where Ng = Ar, Kr, Xe), has been theoretically investigated by state of art all-electron fully relativistic DC-CCSD(T) and DFT calculations with extended basis sets. The main properties of the molecules, including dipole moments and polarizabilities, have been computed and a detailed study of the electron density changes upon formation of the Ng-Au bond has been made. The Ar-Au dissociation energy is found to be nearly the same in both Argon compounds. It almost doubles along the NgAuF series and nearly triples in the corresponding NgAu+ series. The formation of the Ng-Au(I) bonds is accompanied by a large and very complex charge redistribution pattern which not only affects the outer valence region but reaches deep into the core-electron region. The charge transfer from the noble gas to Au taking place in the NgAu+ systems is largely reduced in the fluorides but the Ng-Au chemical bond in the latter systems is found to be tighter near the equilibrium distance. The density difference analysis shows, for all three noble gases, a qualitatively identical nature of the Ng-Au bond, characterized by the pronounced charge accumulation in the middle of the Ng-Au internuclear region which is typical of a covalent bond. This bonding density accumulation is more pronounced in the fluorides, where the Au-F bond is found to become more ionic, while the overall density deformation is more evident and less localized in the NgAu+ systems. Accurate density difference maps and charge-transfer curves help explain very subtle features of the chemistry of Au(l), including its peculiar preference for tight linear bicordination.