Spectroscopic properties and activated mechanism of NO on isolated cationic tantalum clusters: A first-principles...

The adsorption and dissociation of NO on the cationic Ta₁₅⁺ cluster were investigated using the density-functional theory (DFT) calculations, and the Ta-centered bicapped hexagonal antiprism (BHA) structure of cationic Ta₁₅⁺ cluster can be identified as the global minimum, which reproduces well the infrared multiple photo dissociation (IR-MPD) spectrum. Our results show that the cationic BHATa₁₅⁺ cluster provides the hollow region for NO to interact effectively, and possess larger adsorption strength on the region than other sites. The density of states, charge density differences and frontier molecular orbitals were analyzed to understand the electronic properties of the stable NO-adsorbed isomers. The characteristic IR peaks of the firstly two low-lying isomers are properly assigned, in which the strongest IR peak originates from the N - O stretching vibration. For the dissociation of NO on the BHATa₁₅⁺ cluster, it is found that the reaction path II easily occurs rather than path I due to small reaction barrier, and the cluster may possess the great catalytic behavior to dissociate NO molecule. The present results will inevitably stimulate future theoretical and experimental studies for the design of novel Ta-based catalytic materials for the NO dissociation.