Another look at energetically quasi‐degenerate structures of the gold cluster Au₂₇^q with q = 1, 0, −1

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.

A new look at the structure of the neutral Au18 cluster: hollow versus filled golden cage

“…Motivated by their distinctive physico-chemical properties and effective applications in numerous nanometer-size devices, [1][2][3] including chemical/biological sensors, 4 biomedical treatments, [5][6][7] catalysts for chemical reactions, gold and gold-based clusters have been the subject of intensive research in recent decades. [8][9][10][11][12] Significant attention has been devoted to these small systems with the aim to recognize the critical factors that govern their application related properties such as their size and shape. The clusters of gold were found to exhibit intriguing structural arrangements and non-classical bonding features that are strikingly different from those of other transition metals.…”