Journal of Physical Chemistry A, Vol.118, No.10, 1761-1768, 2014
Reactions of Size-Selected Copper Cluster Cations and Anions with Nitric Oxide: Enhancement of Adsorption in Coadsorption with Oxygen
Reactions of size-selected Cu-n +/- and CunOm +/- (n = 3-19, m <= 9) clusters with NO were investigated in the near-thermal energy region under single collision conditions using a tandem-type mass spectrometer with two ion-guided cells. Oxygen atoms preadsorbed on the cluster can significantly enhance the NO adsorption probability and cause additional reactions. NO adsorption is observed particularly for anionic copper cluster dioxides, CunO2- (n >= 8), followed by the release of a Cu atom from CunO2- (n = 8, 10, and 12), which suggests that NO adsorbs strongly, i.e., dissociatively on these clusters. Density functional theory calculations support that dissociative adsorption of NO occurs in the reaction of Cu8O2- under the present experimental conditions. On the other hand, NO oxidation proceeds in reactions of oxygen-rich cluster cations such as Cu4O3+, Cu6O5+, Cu9O7+, and Cu11O8+.