The Critical Number of Gold Atoms for a Metallic State Nanocluster: Resolving a Decades-Long Question

Meng Zhou, Xiangsha Du, He Wang, Rongchao Jin

Research output: Contribution to journalReview articlepeer-review

Abstract

Probing the transition from a metallic state to a molecular state in gold nanoparticles is fundamentally important for understanding the origin of surface plasmon resonance and the nature of the metallic bond. Atomically precise gold nanoclusters are desired for probing such a transition based upon a series of precise sizes with X-ray structures. While the definition of the metallic state in nanoclusters is simple, that is, when the HOMO-LUMO gap (Eg) becomes negligibly small (Eg < kBT, where kB is the Boltzmann constant and T the temperature), the experimental determination of ultrasmall Eg (e.g., of kBT level) is difficult, and the thermal excitation of valence electrons apparently comes into play in ultrasmall Eg nanoclusters. Although a sharp transition from nonmetallic Au246(SR)80 to metallic Au279(SR)84 (SR: thiolate) has been observed, there is still uncertainty about the transition region. Here, we summarize several criteria on determining the metallic state versus the molecular (or nonmetallic) state in gold nanoclusters, including (1) Eg determined by optical and electrochemical methods, (2) steady-state absorption spectra, (3) cryogenic optical spectra, (4) transient absorption spectra, (5) excited-state lifetime and power dependence, and (6) coherent oscillations in ultrafast electron dynamics. We emphasize that multiple analyses should be performed and cross-checked in practice because no single criterion is definitive. We also review the photophysics of several gold nanoclusters with nascent surface plasmon resonance. These criteria are expected to deepen the understanding of the metallic to molecular state transition of gold and other metal nanoclusters and also promote the design of functional nanomaterials and their applications.

Original languageEnglish (US)
Pages (from-to)13980-13992
Number of pages13
JournalACS Nano
Volume15
Issue number9
DOIs
StatePublished - Sep 28 2021

Keywords

  • atomically precise gold nanoclusters
  • coherent oscillations
  • electronic properties
  • excited-state dynamics
  • metal to nonmetal transition
  • photophysics
  • surface plasmon resonance
  • transient absorption

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

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