Silver sulfide nanoclusters and the superatom model

Jing-Qiang Goh, Sami Malola, Hannu Häkkinen, Jaakko Akola

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    7 Citations (Scopus)


    The superatom model of electron-shell closings has been widely used to explain the stability of noble-metal nanoclusters of few nanometers, including thiolate-protected Au and Ag nanoclusters. The presence of core sulfur atoms in silver sulfide (Ag-S) nanoclusters renders them a class of clusters with distinctive properties as compared to typical noble-metal clusters. Here, it is natural to ask whether the superatom model is still applicable for the Ag-S nanoclusters with mixed metal and nonmetal core atoms. To address this question, we applied density functional simulations to analyze a series of Ag-S nanoclusters: Ag14S(SPh)12(PPh3)8, Ag14(SC6H3F2)12(PPh3)8, Ag70S16(SPh)34(PhCO2)4(triphos)4, and [Ag123S35(StBu)50]3+. We observed that superatomic orbitals are still present in the conduction band of these Ag-S clusters where the cluster cores comprise mostly silver atoms. Our Bader charge analysis illustrates that thiolates play a significant role in withdrawing charge (electron density) from the core Ag atoms. The simulated optical absorption properties of the selected Ag-S clusters reflect the substantial band gaps associated with typical molecular orbitals on both sides. Apart from Ag14S(SPh)12(PPh3)8, which has a central sulfur atom in the cluster core, superatomic orbitals of the Ag-S clusters can have contributions for individual transitions in the conduction band.

    Original languageEnglish
    Pages (from-to)1583-1590
    Number of pages8
    JournalJournal of Physical Chemistry C
    Issue number3
    Publication statusPublished - 22 Jan 2015
    Publication typeA1 Journal article-refereed

    Publication forum classification

    • Publication forum level 1

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Electronic, Optical and Magnetic Materials
    • Surfaces, Coatings and Films
    • General Energy


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