Another look at energetically quasi-degenerate structures of the gold cluster Au27q with q = 1, 0, −1

Pham Vu Nhat, Nguyen Thanh Si, Vitaly G. Kiselev, Minh Tho Nguyen

Research output: Contribution to journalArticlepeer-review

Abstract

Quantum chemical computations were used to reinvestigate the geometries, spectroscopic, and energetic properties of the gold clusters Au27q in three charge states (q = 1, 0, −1). Density functional theory (DFT) and the domain-based local pair natural orbital modification of the coupled-cluster theory DLPNO-CCSD(T) calculations revealed that, at variance with earlier reports in the literature, while the anion Au27 tends to exist in a tube-like form, both the lowest-energy Au27 and Au27+ isomers exhibit a pyramidal shape. However, several isomers were found to lie very close in energy, thus rendering a structural transition and their coexistence easy to occur. More specifically, the equilibrium geometry of the neutral Au27 is a core-shell pyramid-like structure with one gold atom located inside. We also identified a novel ground state for the anion Au27 and located for the first time the global minimum of the cation Au27+. The vertical detachment energies of the neutral and anionic states were also computed and used to assign the available experimental photoelectron spectra. Although many Au27 isomers were predicted to be energetically quasi-degenerate, the corresponding distinctive vibrational signatures can be used as fingerprints for the identification of cluster geometrical features.

Original languageEnglish
Pages (from-to)2145-2153
Number of pages9
JournalJournal of Computational Chemistry
Volume42
Issue number30
Early online date26 Aug 2021
DOIs
Publication statusPublished - 15 Nov 2021

OECD FOS+WOS

  • 1.04.DY CHEMISTRY, MULTIDISCIPLINARY
  • 1.04 CHEMICAL SCIENCES

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