The halogen analogs of thiolated gold nanoclusters

Abstract

Is it possible to replace all the thiolates in a thiolated gold nanocluster with halogens while still maintaining the geometry and the electronic structure? In this work, we show from density functional theory that such halogen analogs of thiolated gold nanoclusters are highly likely. Using Au₂₅X₁₈⁻ as an example, where X = F, Cl, Br, or I replaces –SR, we find that Au₂₅Cl₁₈⁻ demonstrates a high similarity to Au₂₅(SR)₁₈⁻ by showing Au–Cl distances, Cl–Au–Cl angles, band gap, and frontier orbitals similar to those in Au₂₅(SR)₁₈⁻. DFT-based global minimization also indicates the energetic preference of staple formation for the Au₂₅Cl₁₈⁻ cluster. The similarity between Au_m(SR)_n and Au_mX_n could be exploited to make viable Au_mX_n clusters and to predict structures for Au_m(SR)_n.