Understanding the Nascent Plasmons and Metallic Bonding in Atomically Precise Gold Nanoclusters

Abstract

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 the success in obtaining atomically precise nanoclusters (NCs) of hundreds of atoms per core. In this work, thiolate-protected Au279(SR)84 and Au333(SR)79 NCs with 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 at r.t. to insulating state at cryogenic temperatures (down to 2.5 K), indicating a nonthermal origin for the 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 the plasmon birth from concerted excitonic transitions.

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Dec 2021
Accepted
13 Jan 2022
First published
13 Jan 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022, Accepted Manuscript

Understanding the Nascent Plasmons and Metallic Bonding in Atomically Precise Gold Nanoclusters

X. Du, Z. Liu, T. Higaki, M. Zhou and R. Jin, Chem. Sci., 2022, Accepted Manuscript , DOI: 10.1039/D1SC06819A

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