TY - JOUR

T1 - Another look at energetically quasi-degenerate structures of the gold cluster Au27q with q = 1, 0, −1

AU - Nhat, Pham Vu

AU - Si, Nguyen Thanh

AU - Kiselev, Vitaly G.

AU - Nguyen, Minh Tho

N1 - Funding Information: This work is funded by VinGroup (Vietnam) and supported by VinGroup Innovation Foundation (VinIF) under project code VinIF.2020.DA21. Funding information: Funding Information: V.G.K. acknowledges the support of this work by the Supercomputer Center of Novosibirsk State University and Irkutsk Supercomputer Center SB RAS through the use of their computational facilities. Publisher Copyright: © 2021 Wiley Periodicals LLC.

PY - 2021/11/15

Y1 - 2021/11/15

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85113363870&partnerID=8YFLogxK

U2 - 10.1002/jcc.26744

DO - 10.1002/jcc.26744

M3 - Article

C2 - 34435682

AN - SCOPUS:85113363870

VL - 42

SP - 2145

EP - 2153

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 30

ER -