Decomposition reactions of NO molecules on gas-phase Rhn+ (n = 6–9) clusters were investigated by gas-phase thermal desorption spectrometry and density functional theory calculations.

The adsorption of an NO molecule on a cationic iridium-doped rhodium cluster, Rh 5 Ir + , was investigated by infrared multiple photon dissociation spectroscopy (IRMPD) of Rh 5 IrNO + • Ar p complexes in the 300−2000 cm −1 spectral range, where the Ar atoms acted as a messenger signaling IR absorption. Complementary density functional theory (DFT) calculations predicted two near-isoenergetic structures as the putative global minimum: one with NO adsorbed in molecular form in the on-top configuration on the Ir atom in Rh 5 Ir + , and one where NO is dissociated with the O atom bound to the Ir atom in the on-top configuration and the N atom on a hollow site formed by three Rh atoms. A comparison between the experimental IRMPD spectrum of Rh 5 IrNO + and calculated spectra indicated that NO mainly adsorbs molecularly on Rh 5 Ir + , but evidence was also found for structures with dissociatively adsorbed NO. The estimated fraction of Rh 5 IrNO + structures with dissociatively adsorbed NO is approximately 10%, which was higher than that found for Rh 6 + , but lower than that for Ir 6 + . The DFT calculations indicated the existence of an energy barrier in the NO dissociation pathway that is exothermic with respect to the reactants, which was considered to prevent NO from dissociating readily on Rh 5 Ir + . The height of the barrier is lower than that for NO dissociation over Rh 6 + , which is attributed to the higher binding energy of atomic O to the Ir atom in Rh 5 Ir + than to a Rh atom in Rh 6 + .