期刊
SMALL
卷 17, 期 39, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/smll.202101855
关键词
alloy clusters; breathing modes; metal clusters; Raman spectroscopy
类别
资金
- University of Geneva
- Swiss National Science Foundation [200020_172511, 200020_192232]
- UEFISCDI [PN-III-P4-ID-PCE-2020-2783, PCE 190/2021]
- Swiss National Science Foundation (SNF) [200020_192232] Funding Source: Swiss National Science Foundation (SNF)
In this study, distinct Raman spectroscopic signatures of the metal core of atomically precise, ligand-protected noble metal nanoclusters are reported using model systems Au-38(PET)(24) and Au38-xAgx(PET)(24). The low-frequency Raman spectra are shown to be a characteristic fingerprint of atomically precise clusters, while the vibrations associated with the outer metal-ligand staple motifs do not shift significantly with increasing Ag content. DFT calculations reveal weak Raman bands at higher frequencies related to the rattling of two central gold atoms of the bi-icosahedral Au-23 core.
Distinct Raman spectroscopic signatures of the metal core of atomically precise, ligand-protected noble metal nanoclusters are reported using Au-38(PET)(24) and Au38-xAgx(PET)(24) (PET = 2-phenylethanethiolate, -SC2H4C6H5) as model systems. The fingerprint Raman features (occurring <200 cm(-1)) of these clusters arise due to the vibrations involving metal atoms of their Au-23 or Au23-xAgx cores. A distinct core breathing vibrational mode of the Au-23 core has been observed at 90 cm(-1). Whereas the breathing mode shifts to higher frequencies with increasing Ag content of the cluster, the vibrational signatures due to the outer metal-ligand staple motifs (between 200 and 500 cm(-1)) do not shift significantly. DFT calculations furthermore reveal weak Raman bands at higher frequencies compared to the breathing mode, which are associated mostly with the rattling of two central gold atoms of the bi-icosahedral Au-23 core. These vibrations are also observed in the experimental spectrum. The study indicates that low-frequency Raman spectra are a characteristic fingerprint of atomically precise clusters, just as electronic absorption spectroscopy, in contrast to the spectrum associated with the ligand shell, which is observed at higher frequencies.
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