Au₆₀^–: The Smallest Gold Cluster with the High-Symmetry Icosahedral Core Au₁₃

Authors

Seema Pande, University of Nebraska - LincolnFollow
Xingao Gong, Fudan University, Shanghai
Lai-Sheng Wang, Brown UniversityFollow
Xiao Cheng Zeng, University of Nebraska - LincolnFollow

ORCID IDs

Lai-Sheng Wang: 0000-0003-1816-5738

Xiao Cheng Zeng: 0000-0003-4672-8585

Date of this Version

2019

Citation

Published in The Journal of Physical Chemistry Letters 10 (2019), pp 1820-1827.

DOI: 10.1021/acs.jpclett.9b00446

Comments

Copyright © 2019 American Chemical Society. Used by permission.

Abstract

Among coinage metal nanoclusters with 55 atoms, only Ag₅₅^– and Cu₅₅^– are the geometric magic-number clusters, as both exhibit icosahedral symmetry. Au₅₅^–, however, exhibits much lower symmetry due largely to the strong relativistic bonding effect. In this study, we collect a much larger population (>10,000 isomers) of low-energy isomers of Au₅₅^– to Au₆₀^– by using the combined density-functional theory and basin-hopping global optimization method. We also include the spin−orbit effect in the density-functional theory computation to achieve simulated photoelectron spectra in quantitative fashion. Remarkably, we uncover that the Au₁₃ core with the highest icosahedral (I_h) symmetry emerges at the size of Au₆₀^–. Stability analysis suggests that Au₅₇^– with 58 valence electrons, an electronic magic number, is the relatively more stable cluster in the size range considered. Overall, in this size range we reveal a compromise between the trend toward having a perfect icosahedral 13-atom core and the strong relativistic bonding effect.