Gas-phase preparation and the stability of superatomic Nb11O15−

Abstract

We report a study of the reactions of pure metal clusters Nb_n⁻ with dioxygen in the gas phase. It is found that the presence of low-concentration dioxygen reactants results in oxygen-addition products, whereas sufficient high-concentration dioxygen enables oxygen-etching reactions giving rise to molecular niobium oxides. Interestingly, in the presence of a suitable gas flow rate of an intermediate dioxygen concentration, a highly selective product Nb₁₁O₁₅⁻ shows up in the mass spectra. Utilizing density functional theory (DFT) calculations, we have discussed the reactivities of Nb_n⁻ (3 ≤ n ≤ 14) clusters with oxygen, and unveiled the reasonable stability of Nb₁₁O₁₅⁻ pertaining to its unique geometric structure with a D_5h Nb@Nb₁₀ core fully protected by 15 bridge-oxygen atoms. The oxygen-passivated Nb@Nb₁₀O₁₅⁻ cluster exhibits a large HOMO–LUMO gap (1.46 eV) and effective multicenter bonds with remarkable superatom orbitals for all the 26 valence electrons of the Nb@Nb₁₀ core corresponding to well-staggered energy levels. We illustrate the superatomic features in the Nb@Nb₁₀ metallic core for which the adaptive natural density partitioning (AdNDP) analysis unveils thirteen 11c–2e bonds. Among them, one of the 11c–2e bonds accounts for the superatomic S orbital, three bonds correspond to superatomic P orbitals, another five display vivid D orbital characteristics, and the remaining four 11c–2e bonds are assigned to F orbital features. In addition, the net atomic charge of the center Nb atom is as high as −0.804 |e| rendering core–shell electrostatic interactions and the shielding effect of the Nb₁₀O₁₅ shell.