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Zusammenfassung:
The mechanism of dissociative D2 adsorption on Ti2O4−, which serves as a model for an oxygen vacancy on a titania surface, is studied using infrared photodissociation spectroscopy in combination with density functional theory calculations and a recently developed single-component artificial force induced reaction method. Ti2O4− readily reacts with D2 under multiple collision conditions in a gas-filled ion trap held at 16 K forming a global minimum-energy structure (DO–Ti–(O)2–Ti(D)–O)−. The highly exergonic reaction proceeds quasi barrier-free via several intermediate species, involving heterolytic D2-bond cleavage followed by D-atom migration. We show that, compared to neutral Ti2O4, the excess negative charge in Ti2O4− is responsible for the substantial lowering of the D2 dissociation barrier, but does not affect the molecular D2 adsorption energy in the initial physisorption step.
