Issue 8, 2018

Exploring the structure evolution and core/ligand structure patterns of a series of large sized thiolate-protected gold clusters Au145-3N(SR)60-2N (N = 1–8): a first principles study

Abstract

The atomic structures of many atomically precise nanosized ligand protected gold clusters have been resolved recently. However, the determination of the atomic structures of large sized ligand protected gold clusters containing metal atoms over ∼100 is still a grand challenge. The lack of structural information of these larger sized clusters has greatly hindered the understanding of the structure evolution and structure–property relations of ligand protected gold nanoclusters. In this work, we theoretically studied the structure evolution of a series of large sized Au145-3N(SR)60-2N (N = 1–8) clusters based on an “[Au2@Au(SR)2] fragmentation” pathway starting from a model Au145(SR)60 cluster. Through comprehensively searching the atomic structure of various clusters and evaluating their stabilities by means of first principles calculations, the stabilization mechanism of experimentally reported Au130(SR)50 and Au133(SR)52 clusters is first rationalized. Our studies indicated that Au130(SR)50 and Au133(SR)52 are two critical sized clusters on which the gold cores underwent configuration transitions between decahedral and icosahedral cores. The energy comparisons of various cluster isomer structures indicated that the Au130(SR)50, Au127(SR)48, Au124(SR)46 and Au121(SR)44 clusters favored a decahedral core, while the Au133(SR)52, Au136(SR)54, Au139(SR)56, and Au142(SR)58 clusters preferred icosahedral gold cores. Furthermore, we also find that the cuboctahedral gold core is less stable in the cluster size region between ∼120 and ∼140 gold atoms. The optical absorption properties and relative thermodynamic stabilities of the Au145-3N(SR)60-2N (N = 1–8) clusters are also surveyed by density functional theory (DFT) and time-dependent DFT calculations.

Graphical abstract: Exploring the structure evolution and core/ligand structure patterns of a series of large sized thiolate-protected gold clusters Au145-3N(SR)60-2N (N = 1–8): a first principles study

Supplementary files

Article information

Article type
Paper
Submitted
26 10 2017
Accepted
16 1 2018
First published
17 1 2018

Nanoscale, 2018,10, 3918-3929

Exploring the structure evolution and core/ligand structure patterns of a series of large sized thiolate-protected gold clusters Au145-3N(SR)60-2N (N = 1–8): a first principles study

P. Wang, L. Xiong, X. Sun, Z. Ma and Y. Pei, Nanoscale, 2018, 10, 3918 DOI: 10.1039/C7NR07980J

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