Metal cluster cation reactions: Carbon monoxide association to Cu+n ions

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Abstract
Copper cluster cations (Cu+n,n=1–14) were produced in a laser vaporization/flow tube apparatus and equilibrated to room temperature. The association rate constants of carbon monoxide onto these ions were measured; low‐pressure, termolecular behavior was observed for the smaller species while for clusters greater than Cu+7, the longer lifetimes due to the increased number of degrees of freedom leads to pressure independence (>0.3 Torr) of the effective bimolecular rates. Unimolecular decay theory (RRKM) is used to explain the overall trend and when intrinsic surface site reactivity is taken into account, excellent agreement with measured reactivity is obtained.