On the catalytic role of Co+ in the oxygen transport activation of N2O by CO

The mechanism of the cyclic reaction N 2 O ( 1 Σ ) + CO ( 1 Σ + ) → N 2 ( 1 Σ g + ) + CO 2 ( 1 Σ g + ) catalyzed by Co+ has been investigated on both triplet and quintet potential energy surfaces (PESs). The reactions were studied by the UB3LYP density functional method and the CCSD(T) theory. The calculated results of different spin PES show that the reaction proceeds in a two-step manner and spin crossing between different PES occurs. The involved crossing between the PES has been discussed by means of the intrinsic reaction coordinate approach used by Yoshizawa et al., and the crossing points were located. Furthermore, the spin–orbit coupling (SOC) is calculated between electronic states of different multiplicities at the crossing points to estimate the intersystem crossing probabilities.