Theoretical survey of the potential energy surface of Ni+ + acetone reaction

Density functional theory calculations have been carried out to explore the potential energy surface (PES) associated with the gas-phase reaction of Ni+ with acetone. The structures and energies of the different stationary points of this PES have been obtained at the B3LYP/6-311++G(d,p) and B3LYP/6-311+G(2df,2pd) levels. The mechanism leading to the loss of C2H6 and CO is analyzed in terms of the topology of PES. Our calculations indicate the reaction of acetone with Ni+ takes place through five elementary steps: encounter complexation, C–C activation, methyl migration, C–C coupling, and nonreactive dissociation, in which the methyl migration process is rate-determining.