Resumen de Carbon dioxide activation by y atom and y+ cation in the gas phase: A density functional theoretical study
De-man Han, Guo-liang Dai, Zhen-zhong Yan, Chuan-Feng Wang, Ai-guo Zhong
The potential energy surfaces for the Y+CO2 and Y++CO2 reactions have been investigated by using the DFT (B3LYP/ECP/6-31 l+G*) level of theory. Both ground and excited state potential energy surfaces are discussed. The present results show that the reaction mechanism is an insertion mechanism along the C-O bond activation branch. The reaction of Y atom with CO2 was shown to occur preferentially on the doublet PES throughout the reaction process. As for the reaction between Y+cation with CO2, it involves potential energy curve-crossing which dramatically affects reaction mechanism. Due to the intersystem crossing existing in the reaction process of Y+with CO2, the intermediate (OY(η2CO))+ may not form. This mechanism is different from that of Y + CO2 system. All our theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.
