The metallic bond is arguably the most intriguing one among the three types of chemical bonds, and the resultant plasmon excitation ( e.g. in gold nanoparticles) has garnered wide interest. Recent progress in nanochemistry has led to success in obtaining atomically precise nanoclusters (NCs) of hundreds of atoms per core. In this work, thiolate-protected Au 279 (SR) 84 and Au 333 (SR) 79 NCs, both in the nascent metallic state are investigated by cryogenic optical spectroscopy down to 2.5 K. At room temperature, both NCs exhibit distinct plasmon resonances, albeit the NCs possess a gap (estimated 0.02–0.03 eV, comparable to thermal energy). Interestingly, we observe no effect on plasmons with the transition from the metallic state at r.t. to the insulating state at cryogenic temperatures (down to 2.5 K), indicating a nonthermal origin for electron-gas formation. The electronic screening-induced birth of metallic state/bonding is discussed. The obtained insights offer deeper understanding of the nascent metallic state and covalent-to-metallic bonding evolution, as well as plasmon birth from concerted excitonic transitions.
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Anomalous phonon relaxation in Au 333 (SR) 79 nanoparticles with nascent plasmons
Research on plasmons of gold nanoparticles has gained broad interest in nanoscience. However, ultrasmall sizes near the metal-to-nonmetal transition regime have not been explored until recently due to major synthetic difficulties. Herein, intriguing electron dynamics in this size regime is observed in atomically precise Au 333 (SR) 79 nanoparticles. Femtosecond transient-absorption spectroscopy reveals an unprecedented relaxation process of 4–5 ps—a fast phonon–phonon relaxation process, together with electron–phonon coupling (∼1 ps) and normal phonon–phonon coupling (>100 ps) processes. Three types of –R capped Au 333 (SR) 79 all exhibit two plasmon-bleaching signals independent of the –R group as well as solvent, indicating plasmon splitting and quantum effect in the ultrasmall core of Au 333 (SR) 79 . This work is expected to stimulate future work on the transition-size regime of nanometals and discovery of behavior of nascent plasmons.
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- Award ID(s):
- 1808675
- NSF-PAR ID:
- 10172590
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 116
- Issue:
- 27
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- 13215 to 13220
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.1904337116
