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

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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 - 2010

ASJC Scopus subject areas

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

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