The Role of the Anchor Atom in the Ligand of the Monolayer-Protected Au25(XR)18- Nanocluster

We present a density functional theory (DFT) investigation On the role of the anchor atom and ligand on the structural, electronic, and optical properties of the anionic Au-25(XR)(18)(-) nanocluster (X = S, Se, Te; R = H, CH3, and (CH2)(2)Ph). Substituting the anchor atom with other group 16 elements induces subtle changes in the Au-Au and Au-X bond lengths and polarization of the covalent bond. The changes in the electronic structure based on substituting both the anchor and R groups are presented through careful analysis of the density of states and theoretical determined optical spectra, We give a detailed side-by-side comparison into the structural, electronic, and optical properties of Au-25(XR)(18)(-) cluster and further explain the diverse role of ligand substitution.