Theoretical study of the reaction of Ni+ with OCS

The reactivity of Ni+ with OCS on both doublet and quartet potential energy surfaces (PES) has been investigated at the B3LYP/6-311+G(d) level. The object of this investigation was the elucidation of the reaction mechanism. The calculated results indicated that both the CS and CO bond activations proceed via an insertion-elimination mechanism. Intersystem crossing between the doublet and quartet surfaces may occur along both the CS and CO bond activation branches. The ground states of NiS+ and NiO+ were found to be quartets, whereas NiCO+ and NiCS+ have doublet ground states. The CS bond activation is energetically much more favorable than the CO bond activation. All theoretical results are in line with early experiments.