Theoretical Study on the Reactions of Pd+ and Pd with CO2 in Gas Phase

Abstract

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 Pd+ cation and Pd atom, for better understanding the mechanism of second-row metal reacting with CO₂. The minimum energy reaction path is found to involve the spin inversion in the different reaction steps. This potential energy curve-crossing dramatically affects reaction energetic. The present results show that the reaction mechanism is insertion-elimination mechanism along the C-O bond activation. All the theoretical results can lead us to understand deeply the mechanism of the reactions of Pd²⁺ and Pd with CO₂ in gas phase and may be helpful for the further experimental investigation of the reaction.