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Abstract

We report on the interaction of carbon monoxide with cationic gold clusters in the gas phase. Successive adsorption of CO molecules on the Au_n⁺ clusters proceeds until a cluster size specific saturation coverage is reached. Structural information for the bare gold clusters is obtained by comparing the saturation stoichiometry with the number of available equivalent sites presented by candidate structures of Au_n⁺. Our findings are in agreement with the planar structures of the Au_n⁺ cluster cations with n≤7 that are suggested by ion mobility experiments [Gilb, S.; Weis, P.; Furche, F.; Ahlrichs, R.; Kappes, M. M. J. Chem. Phys. 2001, 116, 4094]. By inference we also establish the structure of the saturated Au_n(CO_m⁺ complexes. In certain cases we find evidence suggesting that successive adsorption of CO can distort the metal cluster framework. In addition, the vibrational spectra of the Au_n(CO_m⁺ complexes in both the CO stretching region and in the region of the Au-C stretch and the Au-C-O bend are measured using infrared photodepletion spectroscopy. The spectra further aid in the structure determination of Au_n⁺, provide information on the structure of the Au_n⁺-CO complexes, and can be compared with spectra of CO adsorbates on deposited clusters or surfaces.