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

Heehyun Baek; Jiwon Moon; Joonghan Kim

doi:10.1021/acs.jpca.6b11868

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

J Phys Chem A. 2017 Mar 30;121(12):2410-2419. doi: 10.1021/acs.jpca.6b11868. Epub 2017 Mar 21.

Authors

Heehyun Baek¹, Jiwon Moon¹, Joonghan Kim¹

Affiliation

¹ Department of Chemistry, The Catholic University of Korea , Bucheon 14662, Republic of Korea.

PMID: 28291343
DOI: 10.1021/acs.jpca.6b11868

Abstract

Neutral gold clusters, Au_n (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 Au_n (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 Au_n (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.