Observation of earlier two-to-three dimensional structural transition in gold cluster anions by isoelectronic substitution: M Aun- (n=8-11; M=Ag,Cu)

Lei Ming Wang, Rhitankar Pal, Wei Huang, Xiao Cheng Zeng, Lai Sheng Wang

Research output: Contribution to journalArticle

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Abstract

The effects of isoelectronic substitution on the electronic and structural properties of gold clusters are investigated in the critical size range of the two-dimensional (2D)-three-dimensional (3D) structural transition (M Au n-, n=8-11; M=Ag,Cu) using photoelectron spectroscopy and density functional calculations. Photoelectron spectra of M Au n- are found to be similar to those of the bare gold clusters Au n+1 -, indicating that substitution of a Au atom by a Ag or Cu atom does not significantly alter the geometric and electronic structures of the clusters. The only exception occurs at n=10, where very different spectra are observed for M Au 10 - from Au 11 -, suggesting a major structural change in the doped clusters. Our calculations confirm that M Au 8- possesses the same structure as Au 9- with Ag or Cu simply replacing one Au atom in its C2v planar global minimum structure. Two close-lying substitution isomers are observed, one involves the replacement of a center Au atom and another one involves an edge site. For Au 10 - we identify three coexisting low-lying planar isomers along with the D3h global minimum. The coexistence of so many low-lying isomers for the small-sized gold cluster Au 10 - is quite unprecedented. Similar planar structures and isomeric forms are observed for the doped M Au 9- clusters. Although the global minimum of Au 11 - is planar, our calculations suggest that only simulated spectra of 3D structures agree with the observed spectra for M Au 10 -. For M Au 11 -, only a 3D isomer is observed, in contrast to Au 12 - which is the critical size for the 2D-3D structural transition with both the 2D and 3D isomers coexisting. The current work shows that structural perturbations due to even isoelectronic substitution of a single Au atom shift the 2D to 3D structural transition of gold clusters to a smaller size.

Original languageEnglish (US)
Article number114306
JournalJournal of Chemical Physics
Volume132
Issue number11
DOIs
StatePublished - Mar 26 2010

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Gold
Isomers
Anions
Substitution reactions
substitutes
gold
anions
Atoms
isomers
atoms
Photoelectron spectroscopy
Photoelectrons
Electronic properties
Electronic structure
Density functional theory
Structural properties
planar structures
photoelectrons
photoelectron spectroscopy
electronic structure

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Observation of earlier two-to-three dimensional structural transition in gold cluster anions by isoelectronic substitution : M Aun- (n=8-11; M=Ag,Cu). / Wang, Lei Ming; Pal, Rhitankar; Huang, Wei; Zeng, Xiao Cheng; Wang, Lai Sheng.

In: Journal of Chemical Physics, Vol. 132, No. 11, 114306, 26.03.2010.

Research output: Contribution to journalArticle

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abstract = "The effects of isoelectronic substitution on the electronic and structural properties of gold clusters are investigated in the critical size range of the two-dimensional (2D)-three-dimensional (3D) structural transition (M Au n-, n=8-11; M=Ag,Cu) using photoelectron spectroscopy and density functional calculations. Photoelectron spectra of M Au n- are found to be similar to those of the bare gold clusters Au n+1 -, indicating that substitution of a Au atom by a Ag or Cu atom does not significantly alter the geometric and electronic structures of the clusters. The only exception occurs at n=10, where very different spectra are observed for M Au 10 - from Au 11 -, suggesting a major structural change in the doped clusters. Our calculations confirm that M Au 8- possesses the same structure as Au 9- with Ag or Cu simply replacing one Au atom in its C2v planar global minimum structure. Two close-lying substitution isomers are observed, one involves the replacement of a center Au atom and another one involves an edge site. For Au 10 - we identify three coexisting low-lying planar isomers along with the D3h global minimum. The coexistence of so many low-lying isomers for the small-sized gold cluster Au 10 - is quite unprecedented. Similar planar structures and isomeric forms are observed for the doped M Au 9- clusters. Although the global minimum of Au 11 - is planar, our calculations suggest that only simulated spectra of 3D structures agree with the observed spectra for M Au 10 -. For M Au 11 -, only a 3D isomer is observed, in contrast to Au 12 - which is the critical size for the 2D-3D structural transition with both the 2D and 3D isomers coexisting. The current work shows that structural perturbations due to even isoelectronic substitution of a single Au atom shift the 2D to 3D structural transition of gold clusters to a smaller size.",
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AB - The effects of isoelectronic substitution on the electronic and structural properties of gold clusters are investigated in the critical size range of the two-dimensional (2D)-three-dimensional (3D) structural transition (M Au n-, n=8-11; M=Ag,Cu) using photoelectron spectroscopy and density functional calculations. Photoelectron spectra of M Au n- are found to be similar to those of the bare gold clusters Au n+1 -, indicating that substitution of a Au atom by a Ag or Cu atom does not significantly alter the geometric and electronic structures of the clusters. The only exception occurs at n=10, where very different spectra are observed for M Au 10 - from Au 11 -, suggesting a major structural change in the doped clusters. Our calculations confirm that M Au 8- possesses the same structure as Au 9- with Ag or Cu simply replacing one Au atom in its C2v planar global minimum structure. Two close-lying substitution isomers are observed, one involves the replacement of a center Au atom and another one involves an edge site. For Au 10 - we identify three coexisting low-lying planar isomers along with the D3h global minimum. The coexistence of so many low-lying isomers for the small-sized gold cluster Au 10 - is quite unprecedented. Similar planar structures and isomeric forms are observed for the doped M Au 9- clusters. Although the global minimum of Au 11 - is planar, our calculations suggest that only simulated spectra of 3D structures agree with the observed spectra for M Au 10 -. For M Au 11 -, only a 3D isomer is observed, in contrast to Au 12 - which is the critical size for the 2D-3D structural transition with both the 2D and 3D isomers coexisting. The current work shows that structural perturbations due to even isoelectronic substitution of a single Au atom shift the 2D to 3D structural transition of gold clusters to a smaller size.

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