The occurrence of two different chemical reactions initiated by the surface impact of acetone dimer, trimer, and tetramer cations (energy 20–70 eV) on a stainless-steel surface (covered with hydrocarbons) was observed. The reaction product is the protonated acetone ion, formed in (i) an intracluster ion–molecule reaction, and in (ii) a hydrogen pickup reaction of the cluster ion with the surface material. Only the monomer product ions (and small amounts of their dissociation products) could be observed; the spectra did not show any presence of clustered product ions. A simple model based on the Brauman double-well potential is suggested to explain the formation of the two product ions. In accordance with predictions from molecular dynamics simulations, this appears to be the first observation of competitive chemical reactions of a cluster ion driven by energy transfer in a surface collision.

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