Sensitive X-ray Absorption Near Edge Structure Analysis on the Bonding Properties of Au(30)(SR)(18) Nanoclusters

[Image: see text] Au nanoclusters (NCs) with organothiolate protecting ligands are a field of great interest and X-ray absorption spectroscopy is a useful tool for the structure and property studies of these Au NCs. However, the Au NCs normally show broad and low-intensity features in the gold X-ray absorption near-edge structure (XANES) region, lowering the sensitivity of the technique and making it difficult to use for the analysis of Au NCs. In this work we report a sensitive gold L(3)-edge XANES study on the bonding properties of the newly discovered Au(30)(SR)(18) NCs utilizing a combined approach of the first derivative XANES spectra and quantum simulations. First derivative XANES spectra are compared with the well-studied Au(25)(SR)(18) with the aim of determining the unique features of Au(30)(SR)(18). It is found that the early XANES region of the Au NCs is significantly influenced by the gold–gold bonding environment in the surface sites, as the varying surface Au–Au bond lengths in Au(25)(SR)(18) and Au(30)(SR)(18) result in pronounced difference in the first derivative XANES. These findings can be consistently explained using site-selective quantum simulations of the XANES spectra based on the Au NC structural models. The XANES method presented in this work offers a useful tool for the sensitive analysis on structure and bonding properties of Au NCs.