摘要
用密度泛函理论DFT-UB3LYP方法,对2Sr+,2Ba+采用相对论校正赝势基组SDD,对C,N,O采用6-311+G(2d)基组,计算研究了气相中碱土金属离子2Sr+,2Ba+催化N2O(X1∑+)+CO(X1∑+)→N2(X1∑+g)+CO2(X1∑+g)反应的微观机理.优化了二重态势能面上各反应物、中间体和过渡态的构型特征,并用频率分析方法和内禀反应坐标方法(IRC)对过渡态进行了验证.2Sr+和2Ba+转化N2O,CO为N2,CO2的循环催化反应的计算所得结论与实验结果相同,两者的反应路径相似,两步进行的主反应都各包括两个反应通道.并通过分析NBO电荷分布对各反应复合物形成时电荷的变化作了相应讨论.
The reaction mechanism of the reaction N2O（1∑＋）＋CO（1∑＋） → N2（1∑＋g）＋CO2（1∑＋g） cata-lyzed by alkaline-earth metal cations 2Sr＋ and 2Ba＋ have been investigated by using the UB3LYP density functional theory（DFT,UB3LYP） with the relativistic effective core potential（RECP） of basis sets（SDD） for 2Sr＋,2Ba＋ and the 6-311＋G（2d） basis set for C,N and O on doublet energy surfaces.The geometries for reactants,the transition states and the products are completely optimized.All the transition states are verified by the vibrational analysis and the internal reaction coordinate（IRC） calculations.The results show both main reactions process in a two-step manner to products.NBO analysis has been used to discuss the structure of reactant-complexes,our calculated results for the title reactions are in close agreement with ex-perimental observations.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2011年第2期157-162,共6页
Acta Chimica Sinica
