Sharp Transition from Nonmetallic Au₂₄₆ to Metallic Au₂₇₉ with Nascent Surface Plasmon Resonance

The optical properties of metal nanoparticles have attracted wide interest. Recent progress in controlling nanoparticles with atomic precision (often called nanoclusters) provide new opportunities for investigating many fundamental questions, such as the transition from excitonic to plasmonic state, which is a central question in metal nanoparticle research because it provides insights into the origin of surface plasmon resonance (SPR) as well as the formation of metallic bond. However, this question still remains elusive because of the extreme difficulty in preparing atomically precise nanoparticles larger than 2 nm. Here we report the synthesis and optical properties of an atomically precise Au₂₇₉(SR)₈₄ nanocluster. Femtosecond transient absorption spectroscopic analysis reveals that the Au₂₇₉ nanocluster shows a laser power dependence in its excited state lifetime, indicating metallic state of the particle, in contrast with the nonmetallic electronic structure of the Au₂₄₆(SR)₈₀ nanocluster. Steady-state absorption spectra reveal that the nascent plasmon band of Au₂₇₉ at 506 nm shows no peak shift even down to 60 K, consistent with plasmon behavior. The sharp transition from nonmetallic Au₂₄₆ to metallic Au₂₇₉ is surprising and will stimulate future theoretical work on the transition and many other relevant issues.