Aun (n = 1,11) Clusters Interacting With Lone-Pair Ligands

We analyze the pattern of binding energies (BEs) of small Aun clusters (n = 1–7, 11) with lone-pair ligands (L = H2O, SH2, NH3, PH3, PF3, PCl3, and PMe3) employing the density functional theory. We use PBE0 functional with the dispersion correction and scalar relativistic effective core potential. This approach provides correct BEs when compared with benchmark CCSD­(T) calculations for Au–L and Au2–L complexes. The pattern of BEs of Aun–L complexes is irregular with BE for Au3 ≈ Au4 > Au2 > Au7 > Au5 > Au11 > Au6 > Au1. Electron affinities (EAs) of Aun clusters exhibit oscillatory pattern with the cluster size. Binding energies of Aun–L complexes are oscillatory as well following EAs of Aun clusters. BEs of odd and even Aun–L complexes were analyzed separately. The bonding mechanism in odd Aun–L complexes is dominated by the lone pair → metal electron donation to the singly occupied valence Aun orbital accompanied by the back–donation. Even Aun clusters create covalent Aun–L bonds with BEs higher than those in odd Aun–L complexes. The BEs pattern and optimized geometries of Aun–L complexes correspond to the picture of creating the gold–ligand bond through the lone pair of a ligand interacting with the singly occupied molecular orbital in odd clusters or lowest unoccupied molecular orbital in even clusters of Aun. Ligands in both odd and even Aun–L complexes form three groups with binding energies that correlate with their ionization energies. The lowest BE is calculated for H2O as a ligand, followed by SH2 and NH3. PX3 ligands exhibit highest BEs.