Comparison of Hydrogen and Gold Bonding in [XHX]-, [XAuX]-, and Isoelectronic [NgHNg]+, [NgAuNg]+ (X=Halogen, Ng=Noble Gas)

Quantum chemical calculations at the MP2/aug-cc- pVTZ and CCSD(T)/aug-cc-pVTZ levels have been carried out for the title compounds. The electronic structures were analyzed with a variety of charge and energy partitioning methods. All molecules possess linear equilibrium structures with D-infinity h symmetry. The total bond dissociation energies (BDEs) of the strongly bonded halogen anions [XHX](-) and [XAuX](-) decrease from [FHF](-) to [IHI](-) and from [FAuF](-) to [IAuI](-). The BDEs of the noble gas compounds [NgHNg](+) and [NgAuNg](+) become larger for the heavier atoms. The central hydrogen and gold atoms carry partial positive charges in the cations and even in the anions, except for [IAuI](-), in which case the gold atom has a small negative charge of -0.03 e. The molecular electrostatic potentials reveal that the regions of the most positive or negative charges may not agree with the partial charges of the atoms, because the spatial distribution of the electronic charge needs to be considered. The bonding analysis with the QTAIM method suggests a significant covalent character for the hydrogen bonds to the noble gas atoms in [NgHNg](+) and to the halogen atoms in [XHX](-). The covalent character of the bonding in the gold systems [NgAuNg](+) and [XAuX](-) is smaller than in the hydrogen compound. The energy decomposition analysis suggests that the lighter hydrogen systems possess dative bonds X--> H+<- X- or Ng -> H+<- Ng while the heavier homologues exhibit electron sharing through two-electron, three-center bonds. Dative bonds X--> Au+<- X- and Ng -> Au+<- Ng are also diagnosed for the lighter gold systems, but the heavier compounds possess electron-shared bonds.