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From Superatomic Au25(SR)18- to Superatomic M@Au24(SR)18q Core-shell Clusters.

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic8024588· OSTI ID:962998

Au{sub 25}(SR){sub 18}{sup -} belongs to a new type of superatom that features an icosahedral Au{sub 13} core-shell structure and a protective layer of six RS(Au-SR){sub 2} motifs. This superatom has a magic number of 8 free electrons that fully fill the 1s and 1p levels of the electron-shell model. By applying this superatom concept to the core-substitution chemistry of Au{sub 25}(SR){sub 18}{sup -}, we first scanned the periodic table for the potential core atom M by applying a simple rule derived from the 8-electron count and then optimized the selected candidates by density functional theory calculations to create many series of M{at}Au{sub 24}(SR){sub 18}{sup q} core-shell nanoclusters. We found that 16 elements from groups 1, 2, and 10-14 of the periodic table can maintain both electronic and geometric structures of the original Au{sub 25}(SR){sub 18}{sup -} magic cluster, indicating that the electron-counting rule based on the superatom concept is powerful in predicting viable M{at}Au{sub 24}(SR){sub 18}{sup q} clusters. Our work opens up a promising area for experimental exploration.

Research Organization:
Oak Ridge National Laboratory (ORNL)
Sponsoring Organization:
SC USDOE - Office of Science (SC)
DOE Contract Number:
AC05-00OR22725
OSTI ID:
962998
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 48; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English

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