Computational study on the molecular structures and photoelectron spectra of bimetallic oxide clusters MW2O9-/0 (M = V, Nb, Ta)

Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are carried out to investigate the electronic and structural properties of a series of bimetallic oxide clusters MW2O9-/0 (M = V, Nb, Ta). Generalized Koopmans’ theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level yield singlet and doublet ground states for the bimetallic anionic and neutral clusters, respectively. All the clusters present the six-membered ring structures with different symmetries, except that the TaW2O9- cluster shows a chained style with a penta-coordinated tantalum atom. Spin density analyses reveal oxygen radical species in all neutral clusters, consistent with their structural characteristics. Moreover, additional calculations are performed to study the oxidation reaction of CO molecule with the W3O9+ cation and the isoelectronic VW2O9 cluster, and results indicate that the introduction of vanadium at tungsten site can efficiently improve the oxidation reactivity.

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► The TaW2O9- cluster shows a chained style with a penta-coordinated tantalum atom.
► Generalized Koopmans’ theorem is applied to simulate the photoelectron spectra.
► We report some interesting radical species with high electron affinities.
► Introduction of V atom at W site can efficiently improve the oxidative reactivity.