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Abstract

Far- and mid-infrared multiple photon dissociation spectroscopy has been employed to study both the structure and surface reactivity of isolated cationic rhodium clusters with surface-adsorbed nitrous oxide, RhnN₂O⁺ (n = 4−8). Comparison of experimental spectra recorded using the argon atom tagging method with those calculated using density functional theory (DFT) reveals that the nitrous oxide is molecularly bound on the rhodium cluster via the terminal N-atom. Binding is thought to occur exclusively on atop sites with the rhodium clusters adopting close-packed structures. In related, but conceptually different experiments, infrared pumping of the vibrational modes corresponding with the normal modes of the adsorbed N₂O has been observed to result in the decomposition of the N₂O moiety and the production of oxide clusters. This cluster surface chemistry is observed for all cluster sizes studied except for n = 5. Plausible N₂O decomposition mechanisms are given based on DFT calculations using exchange-correlation functionals. Similar experiments pumping the Rh−O stretch in Rh_nON₂O⁺ complexes, on which the same chemistry is observed, confirm the thermal nature of this reaction.