Comment on ‘Structural characterization, reactivity and vibrational properties of silver clusters: a new global minimum for Ag16’ by P. L. Rodríguez-Kessler, A. R. Rodríguez-Domínguez, D. MacLeod Carey and A. Muñoz-Castro, Phys. Chem. Chem. Phys., 2020, 22, 27255, DOI: D0CP04018E

Abstract

A recent paper by Rodríguez-Kessler et al., Phys. Chem. Chem. Phys., 2020, 22, 27255–27262, reported not only results of quantum chemical computations (using the PW91 density functional) on Ag₁₆ clusters as emphasized in the article's title, but also on the Ag₁₅ size. These authors confirmed previous results obtained by McKee and Samokhvalov (J. Phys. Chem. A, 2017, 121, 5018–5028 using the M06 density functional) that the most stable isomer of Ag₁₅ is a C_2v structure. We wish to point out that two low symmetry isomers of Ag₁₅ that have a similar energy content are even lower in energy than their reported C_2v global minimum. The relative energies between low-lying Ag₁₅ isomers were again found to be method-dependent, and within the expected accuracy of DFT and CCSD(T) methods they could be considered as energetically degenerate, and likely coexist in a molecular beam. The new lower-energy Ag₁₅ isomers appear to fit more consistently within the structural evolution of small silver clusters.