Coinage Metal Superatomic Cores

Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations

Franck Gam, Dayan Paez-Hernandez, Ramiro Arratia-Perez, C. W. Liu, Samia Kahlal, Jean Yves Saillard, Alvaro Muñoz-Castro

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Coinage-metal atomically precise nanoclusters are made of a well-defined metallic core embedded in a ligand-protecting outer shell. Whereas gold derivatives are particularly well documented, examples of silver nanoclusters are somewhat limited and copper species remain particularly scare. Our DFT relativistic calculations on superatomic metallic cores indicate that copper species are almost as stable as gold clusters and more stable than their silver counterparts. Thus, for silver superatomic cores, the role of the stabilizing ligands is more crucial in the stabilization of the overall structure, in comparison to copper and gold. Hence, the chemistry of the earlier counterparts of gold, especially copper, should grow quickly with at least characterizations of species related to that found in the heavier elements in the triad, which requires tackling synthetic challenges. Time-dependent (TD)-DFT calculations show that with an increase of the cluster core nuclearity, the absorption bands are redshifted, allowing us to differentiate between the clusters types. Moreover, the optical properties of the silver cores are fairly different from that of their Cu and Au relatives.

Original languageEnglish
Pages (from-to)11330-11337
Number of pages8
JournalChemistry - A European Journal
Volume23
Issue number47
DOIs
Publication statusPublished - 22 Aug 2017

Fingerprint

Coinage
Silver
Discrete Fourier transforms
Gold
Copper
Optical properties
Metals
Nanoclusters
Ligands
Absorption spectra
Stabilization
Derivatives

Keywords

  • coinage metals
  • intrinsic stability
  • nanoclusters
  • superatomic cores

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Coinage Metal Superatomic Cores: Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations",
abstract = "Coinage-metal atomically precise nanoclusters are made of a well-defined metallic core embedded in a ligand-protecting outer shell. Whereas gold derivatives are particularly well documented, examples of silver nanoclusters are somewhat limited and copper species remain particularly scare. Our DFT relativistic calculations on superatomic metallic cores indicate that copper species are almost as stable as gold clusters and more stable than their silver counterparts. Thus, for silver superatomic cores, the role of the stabilizing ligands is more crucial in the stabilization of the overall structure, in comparison to copper and gold. Hence, the chemistry of the earlier counterparts of gold, especially copper, should grow quickly with at least characterizations of species related to that found in the heavier elements in the triad, which requires tackling synthetic challenges. Time-dependent (TD)-DFT calculations show that with an increase of the cluster core nuclearity, the absorption bands are redshifted, allowing us to differentiate between the clusters types. Moreover, the optical properties of the silver cores are fairly different from that of their Cu and Au relatives.",
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Coinage Metal Superatomic Cores : Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations. / Gam, Franck; Paez-Hernandez, Dayan; Arratia-Perez, Ramiro; Liu, C. W.; Kahlal, Samia; Saillard, Jean Yves; Muñoz-Castro, Alvaro.

In: Chemistry - A European Journal, Vol. 23, No. 47, 22.08.2017, p. 11330-11337.

Research output: Contribution to journalArticle

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AU - Gam, Franck

AU - Paez-Hernandez, Dayan

AU - Arratia-Perez, Ramiro

AU - Liu, C. W.

AU - Kahlal, Samia

AU - Saillard, Jean Yves

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