Reaction of nitric oxide molecules on transition-metal-doped silver cluster cations: size- and dopant-dependent reaction pathways

Abstract

We report size- and dopant-dependent reaction pathways as well as reactivity of gas-phase free Ag_nM⁺ (M = Sc–Ni) clusters interacting with NO. The reactivity of Ag_nM⁺, except for M = Cr and Mn, exhibits a minimum at a specific size, where the cluster cation possesses 18 or 20 valence electrons consisting of Ag 5s and dopant's 3d and 4s. The product ions range from NO adducts, Ag_nM(NO)_m⁺, and oxygen adducts, Ag_nMO_m⁺, to NO₂ adducts, Ag_nM(NO₂)_m⁺. At small sizes, Ag_nMO_m⁺ are the major products for M = Sc–V, whereas Ag_nM(NO)_m⁺ dominate the products for M = Cr–Ni in striking contrast. In both cases, these reaction products are reminiscent of those from an atomic transition metal. However, the reaction pathways are different at least for M = Sc and Ti; kinetics measurements reveal that the present oxygen adducts are formed via NO adducts, while, for example, Ti⁺ is known to produce TiO⁺ directly by reaction with a single NO molecule. At larger sizes, on the other hand, Ag_nM(NO₂)_m⁺ are dominantly produced regardless of the dopant element because the dopant atom is encapsulated by the Ag host; the NO₂ formation on the cluster is similar to that reported for undoped Ag_n⁺.