title: Structural Evolution of Core-Shell Gold Nanoclusters: Aun-(n = 42-50).
abstract: Gold nanoclusters have attracted great attention in the past decade due to their remarkable size-dependent electronic, optical, and catalytic properties. However, the structures of large gold clusters are still not well-known because of the challenges in global structural searches. Here we report a joint photoelectron spectroscopy (PES) and theoretical study of the structural evolution of negatively charged core-shell gold nanoclusters (Aun-) for n = 42-50. Photoelectron spectra of size-selected Aun-clusters are well resolved with distinct spectral features, suggesting a dominating structural type. The combined PES data and density functional calculations allow us to systematically identify the global minimum or candidates of the global minima of these relatively large gold nanoclusters, which are found to possess low-symmetry structures with gradually increasing core sizes. Remarkably, the four-atom tetrahedral core, observed first in Au33-, continues to be highly robust and is even present in clusters as large as Au42-. Starting from Au43-, a five-atom trigonal bipyramidal core appears and persists until Au47-. Au48-possesses a six-atom core, while Au49-and Au50-feature seven- and eight-atom cores, respectively. Notably, both Au46-and Au47-contain a pyramidal Au20motif, which is stacked with another truncated pyramid by sharing a common 10-atom triangular face. The present study sheds light on our understanding of the structural evolution of the medium-sized gold nanoclusters, the shells and core as well as how the core-shell structures may start to embrace the golden pyramid (bulk-like) fragment.
authors: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.
authors: Seema
authors: S
authors: Pande
authors: Department of Chemistry, Brown University , Providence, Rhode Island 02912, United States.
authors: Wei
authors: W
authors: Huang
authors: Department of Physics, University of Nebraska-Omaha , Omaha, Nebraska 68182, United States.
authors: Nan
authors: N
authors: Shao
authors: Department of Chemistry, Brown University , Providence, Rhode Island 02912, United States.
authors: Lei-Ming
authors: LM
authors: Wang
authors: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.
authors: Navneet
authors: N
authors: Khetrapal
authors: Department of Physics, University of Nebraska-Omaha , Omaha, Nebraska 68182, United States.
authors: Wai-Ning
authors: WN
authors: Mei
authors: Department of Chemistry, Brown University , Providence, Rhode Island 02912, United States.
authors: Tian
authors: T
authors: Jian
authors: Department of Chemistry, Brown University , Providence, Rhode Island 02912, United States.
authors: Lai-Sheng
authors: LS
authors: Wang
authors: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.
authors: Xiao Cheng
authors: XC
authors: Zeng
keywords: core−shell structures; gold anion clusters; gold nanoclusters; photoelectron spectroscopy; structural evolution