Structure of small yttrium monoxide clusters, chemical bonding, and photoionization: threshold photoionization and density functional theory investigations†

Abstract

The photoionization (PI) spectra of small gas-phase yttrium monoxide clusters, Y_nO (n = 1–8), are investigated, and the adiabatic ionization energies are determined. The stable structures are obtained from density functional theory (DFT) calculations. The ground state structures are further confirmed by the CCSD(T) method. The PI spectra are calculated for these stable structures and are compared with the experimental PI spectra. The ground-state structures of the neutral and cation clusters are experimentally assigned with confidence on the basis of a favourable agreement between the experimental and calculated PI spectra. New structures are proposed for Y₂O, Y₆O, and Y₈O compared to the previous literature. Y₂O is a linear molecule in the ground state that was previously proposed as a C_2v bent molecule. The Y_nO clusters become 3-dimensional from n ≥ 3. The O atom stays outside, bridging a triangular face of yttrium clusters. Chemical bonding between the yttrium and oxygen atoms is mostly ionic. The excess charge on the oxygen atom is around 1.4e⁻, transferred from the yttrium atoms bonded with it. Yttrium atoms are mostly covalently bonded. However, for the bigger clusters, free charges of both polarities appear on yttrium atoms that are not bonded with oxygen, indicating ionic interactions. Frontier orbitals consist of mainly delocalized 4d electrons with some 5s contributions, forming Y–Y bonding interactions, but with little contribution and zero contribution from the oxygen orbitals, regardless of the cluster size. The lost electron of Y_nO⁺ mostly comes from the 5s orbitals of all Y atoms in the cluster up to size n = 4, and then from 4d–5s hybrid orbitals from n ≥ 5, with the d contribution increasing with size. This is contrary to the previous view in the literature that photoionization occurs from a localized 4d orbital.