Abstract
We explored the size-dependent reactivity of Agn+ (n = 2-22) with O2 under mild conditions and found that only a few sizes of Agn+, with even values of n = 4, 6, 12, 16, 18, and 22, are reactive. Possible structures of Agn+ (n = 2-22) were determined using a genetic algorithm with incomplete local optimizations at the DFT level, and the calculated bonding strengths of O2 on these structures are consistent with experimental observations. Analyses revealed a close relationship between the reactivity of Agn+ with O2 and its HOMO-LUMO gap: cationic silver clusters with a small HOMO-LUMO gap are reactive, which can be rationalized by the covalent character of chemical bonds between Agn+ and O2 involving their frontier orbitals. The peculiar size-dependent HOMO-LUMO gaps and reactivity with O2 correlate with the subtle interplay between the electronic configurations and geometric structures of these silver cluster cations.
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