Probing the Electronic Properties of W3Ox–/0 (x = 0–2) and W32– Clusters: The Aromaticity of W3 and W32–

Abstract

Density functional theory (DFT) calculations are employed to investigate the structural and electronic properties of bare tritungsten clusters (W3, W3(-), W3(2-)) and tritungsten oxide clusters W3Ox(-/0) (x = 1, 2). Generalized Koopmans' theorem is applied to predict the vertical detachment energies and simulate the photoelectron spectra (PES) for W3Ox(-) (x = 0-2) clusters. Extensive DFT calculations are performed in search of the lowest energy structures for both the anions and the neutrals. The bare tritungsten clusters are predicted to be triangular structures with D3h ((3)A1'), C2v ((2)A1) and D3h ((1)A1') symmetry for W3, W3(-) and W3(2-), respectively. For W3O(-) and W3O clusters, the oxygen atom occupies the terminal site, while the next added oxygen atom is found to be a bridging one in both W3O2(-) and W3O2 clusters. Molecular orbital analyses are carried out to elucidate the chemical bonding of these clusters and provide insights into the sequential oxidation from W3(-) to W3O2(-). Partial σ- and δ-aromaticity are revealed in the neutral W3 (D3h, (3)A1'), while the anion W3(2-) (D3h, (1)A1') possesses only δ-aromaticity.