Gas phase reactivity of size‐selected nickel cluster ions with carbon monoxide has been studied in a triple quadrupole mass spectrometer. Intensity distributions of the various nickel carbonyl ions are measured. Irradiation with a cw Ar+ laser beam demonstrates that efficient detachment of CO ligands occurs following single photon absorption by the metal cluster core. Laser‐induced photodesorption is used to counterbalance the adsorption processes, in order to control the molecular coverage of the metal cluster. Time‐resolved measurements of the kinetics of these two competing processes have been performed. A rate equation model is proposed which brings a detailed understanding of the kinetics and allows derivation of numerical values for the chemisorption rate constant and for the photoabsorption cross section.

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