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Silver sulfide nanoclusters and the superatom model

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Silver sulfide nanoclusters and the superatom model. / Goh, Jing-Qiang; Malola, Sami; Häkkinen, Hannu; Akola, Jaakko.

In: Journal of Physical Chemistry C, Vol. 119, No. 3, 22.01.2015, p. 1583-1590.

Research output: Contribution to journalArticleScientificpeer-review

Harvard

Goh, J-Q, Malola, S, Häkkinen, H & Akola, J 2015, 'Silver sulfide nanoclusters and the superatom model', Journal of Physical Chemistry C, vol. 119, no. 3, pp. 1583-1590. https://doi.org/10.1021/jp511037x

APA

Goh, J-Q., Malola, S., Häkkinen, H., & Akola, J. (2015). Silver sulfide nanoclusters and the superatom model. Journal of Physical Chemistry C, 119(3), 1583-1590. https://doi.org/10.1021/jp511037x

Vancouver

Goh J-Q, Malola S, Häkkinen H, Akola J. Silver sulfide nanoclusters and the superatom model. Journal of Physical Chemistry C. 2015 Jan 22;119(3):1583-1590. https://doi.org/10.1021/jp511037x

Author

Goh, Jing-Qiang ; Malola, Sami ; Häkkinen, Hannu ; Akola, Jaakko. / Silver sulfide nanoclusters and the superatom model. In: Journal of Physical Chemistry C. 2015 ; Vol. 119, No. 3. pp. 1583-1590.

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@article{6d7039d8c6684ba68cac69c5e8929bda,
title = "Silver sulfide nanoclusters and the superatom model",
abstract = "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.",
author = "Jing-Qiang Goh and Sami Malola and Hannu H{\"a}kkinen and Jaakko Akola",
year = "2015",
month = "1",
day = "22",
doi = "10.1021/jp511037x",
language = "English",
volume = "119",
pages = "1583--1590",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society ACS",
number = "3",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - Silver sulfide nanoclusters and the superatom model

AU - Goh, Jing-Qiang

AU - Malola, Sami

AU - Häkkinen, Hannu

AU - Akola, Jaakko

PY - 2015/1/22

Y1 - 2015/1/22

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84921476515&partnerID=8YFLogxK

U2 - 10.1021/jp511037x

DO - 10.1021/jp511037x

M3 - Article

VL - 119

SP - 1583

EP - 1590

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 3

ER -