Reply to the ‘Comment on “Realization of the Zn ³⁺ oxidation state”’ by Y. Shang, N. Shu, Z. Zhang, P. Yang and J. Xu, Nanoscale , 2022, 14 , DOI: 10.1039/D1NR07031B

In a recent paper (https://doi.org/10.1039/D1NR02816B), we suggested that Zn can assume a +3-oxidation state when interacting with super-electrophilic clusters, BeB₁₁(CN)₁₂ and BeB₂₃(CN)₂₂. In a comment to our paper (https://doi.org/10.1039/D1NR07031B), Shang et al. have questioned this suggestion. Using density functional theory with the TPSSh functional and def2-SVP basis sets in the Gaussian16 software and semiempirical localized orbital bonding analysis (LOBA), the authors have made three major claims: (1) the oxidation state of Zn in Zn[BeB₁₁(CN)₁₂] and Zn[BeB₂₃(CN)₂₂] is +2; (2) electron affinities are not reliable to probe the oxidation states; and (3) our results are "misleading" because these are based on the VASP code. According to these authors, VASP is not suitable for small clusters because it uses projected augmented wave (PAW) pseudopotentials. In the following, we show that these claims are invalid, caused by both misunderstanding and the authors' use of a lower-level theory.