Resonance Enhancement of Nonlinear Optical Scattering in Monolayer-Protected Gold Clusters

Monolayer-protected metal clusters (MPCs) have recently gained significant research interest, since they are promising candidates for various applications in bioimaging and catalysis. Besides this, MPCs promise to aid in understanding the evolution of the metallic state from bottom-up principles. MPCs can be prepared with atomic precision, and their nonscalable properties (indicating molecule-like behavior) have been studied with a variety of techniques both theoretically and experimentally. Here, we present spectrally resolved second-order nonlinear optical scattering experiments on thiolate-protected gold clusters (Au₁₃₀(SR)₅₀, Au₁₄₄(SR)₆₀, and Au₅₀₀(SR)₁₂₀). The three clusters share common resonance enhancement around 490 nm, which is ascribed to an interband transition. This indicates emerging metal-like properties, and we tentatively assign the onset of metal-like behavior somewhere between 102 and 130 gold atoms.