Adsorption Kinetics of Nitrogen Molecules on Size-Selected Silver Cluster Cations

We present adsorption processes of dinitrogen on size-selected silver cluster cations, Agn+ (n = 1–10), studied by kinetics measurement using an ion trap. The cluster ions showed sequential adsorption of N2 molecules when the ion trap was cooled down to 105 K, excluding n = 8 and 9 that were exceptionally inactive at this temperature. Termolecular rate coefficients of each adsorption step are determined by analyzing time-dependent changes in the reactant and product ion signals. The first-step rate coefficients were found to increase exponentially from n = 1 to 7 due to increased internal degrees of freedom at larger sizes, which are favorable for accommodating the adsorption energy in a free cluster. In contrast, the adsorption rate turned to decrease for n > 7 due to weaker binding of dinitrogen as revealed by density-functional-theory (DFT) calculation. Adsorption sites on Agn+ are further discussed on the basis of the maximum number of adsorbing N2 molecules observed in the experiment.