Abstract：The reactions of Y＋, Zr＋, Nb＋with CO2, producing the metal oxide ion and CO, are taken as a representative examples to elucidate the overall mechanisms of reactions of second-row early transition metal ions with CO2. The reactions in both ground and excited states are studied by using the UB3LYP density functional method with the Stuttgart pseudopotentials and corresponding basis sets for the metals and the standard 6-311＋G(2d) basis sets for C and O. The geometries for reactants, the transition states and the products are completely optimized. The result shows that the reaction mechanism between second-row early transition metal ions and CO2 is an insertion-elimination mechanism. The potential energy curve crossings, which dramatically affect reaction mechanisms, are discussed in detail. The reactions are all exothermic due to the participation of the metal ions, to be compared with the strong endothermic process of the unimolecular CO2 decomposition.
王永成, 杨晓燕, 耿志远, 刘泽玉, 陈晓霞, 高立国. 气相中Y＋, Zr＋, Nb＋与CO2反应的理论研究[J]. 化学学报, 2006, 64(23): 2310-2316.
WANG Yong-Cheng*; YANG Xiao-Yan; GENG Zhi-Yuan; LIU Ze-Yu; CHEN Xiao-Xia; GAO Li-Guo. Theoretical Study of the Reaction of Y＋, Zr＋, Nb＋ with CO2 in Gas Phase. Acta Chimica Sinica, 2006, 64(23): 2310-2316.