Benchmark Study of Density Functional Theory for Neutral Gold Clusters, Aun (n = 2-8).

Neutral gold clusters, Aun (n = 2-8), were optimized using coupled cluster singles and doubles with perturbative triples (CCSD(T)) with a triple-ζ-level basis set to develop reliable reference values for their structural and energy parameters in order to assess the performance of density functionals. The performance of 44 density functional theory (DFT) methods for calculating molecular structures and relative energies is assessed with respect to CCSD(T). In addition, their performance when calculating vertical ionization potentials (vIPs) of Aun (n = 2-8) is also assessed by comparison with experimental values. The revTPSS functional shows good performance for calculating both the structural and energy properties of Aun (n = 2-8), whereas B3P86 shows a remarkable performance in calculating the vIPs. The quadruple-ζ-level valence basis set is necessary for obtaining accurate energy values in CCSD(T) calculations.