Theoretical study on the reactions of Zr+ and Zr with CO2 in gas phase

Density functional theory (DFT) calculations have been performed to explore the potential energy surfaces of C-O bond activation in CO2 molecule by gas-phase Zr+ cation and Zr atom, for better understanding the mechanism of second-row transition metal reacting with CO2. The minimum energy reaction path is found to involve the spin inversion in the different reaction steps. This potential energy curvecrossing dramatically affects reaction energetics. The present results show that the reaction mechanism is insertion-elimination mechanism along the C-O bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.