Interaction of vanadium oxide cluster anions with water: An experimental and theoretical study on reactivity and mechanism

Vanadium oxide cluster anions (V _xO _y ^-, x = 2-3; y = 3-7) are produced by laser ablation and reacted with water in a fast flow reactor. A time-of-flight mass spectrometer is used to detect the cluster distribution before and after the reactions. Reaction channels of molecular hydrogen elimination (for V _2,3O ₃ ^-), water association (for V ₂O ₅ ^- and V ₃O _6,7 ^-) and the coexistence of both channels (for V ₂O ₄ ^- and V ₃O _4,5 ^-) are observed. V ₂O ₆ ^- and V ₃O ₈ ^- are nearly inert toward water. Density functional theory (DFT) calculations are performed to study the reaction mechanism of V ₂O ₃ ^- in different spin states with water and the results support the experimental observation. The reaction mechanism of V ₂O ₃ ⁺ with water is also studied, which is in agreement with the experimental report in previous literature [Eur. J. Inorg. Chem., 2008, 4961] that molecular hydrogen elimination is a minor reaction channel for V ₂O ₃ ⁺ + H ₂O. The influence of cluster charge states and oxidation states of vanadium atoms on the cluster reactivity are presented based on the experimental and theoretical studies.