A first principles study of thiol-capped Au nanoparticles: Structural, electronic, and magnetic properties as a function of thiol coverage

We have studied the stability of thiolated Au₃₈ nanoparticles (NPs) via density functional theory based calculations varying the coverage from 0 up to 32 molecules. Three different initial core arrangements were considered for the cluster, spherical, tubular, and bi-icosahedral, while thiol groups were attached to the cluster via the sulfur atom either as single molecules or forming more complex staple motifs. After molecular dynamics runs several metastable configurations are found at each coverage thus allowing to analyze the properties of the NPs in the form of ensemble averages. In particular, we address the structural and electronic properties as a function of the number of thiols. The study emphasizes the strong influence of the core structure on the stability of the NPs, and its interplay with the thiol coverage and adsorption geometries. The magnetic properties of the NPs have also been explored via spin-polarized calculations including spin-orbit coupling. No evidence for the existence of a robust intrinsic ferromagnetism is found in any of the structures.