气相中环丁烯负离子与N_2O反应机理的理论研究  

Theoretical Study on the Reaction Mechanism of Cyclobutene Anion with N_2O in Gas Phase

作　　者：耿志远[1] 梁俊玺[1] 王永成[1] 韩彦霞[1] 闫盆吉[1] 

机构地区：[1]西北师范大学化学化工学院甘肃省高分子材料重点实验室,兰州730070

出　　处：《化学学报》2008年第3期325-334,共10页Acta Chimica Sinica

摘　　要：采用MP2和B3LYP两种计算方法,在6-31++G(d,p)的基组下,对气相中环丁烯负离子与N2O反应的微观机理进行了较为系统的计算研究,并在相同基组下进一步用QCISD方法在MP2优化构型的基础上进行了单点能校正.结果表明,该反应存在两条反应通道,每条反应通道又包含着三条反应路径,产物分别为乙烯基重氮甲基负离子与甲醛,同时也应能检测到少量的环丁烯酮负离子及N2等产物.其中,通道1是主反应通道,路径1为主反应路径,路径3是路径1和2的竞争反应.理论计算结果与实验预测基本一致.The mechanism for the ion-molecule reaction of cyclobutene anion with nitrous oxide in gas phase has been characterized in detail. Based on 6-31 ＋＋G（d,p） basis set, using the second-order MФller-Plesset perturbation theory （MP2） and comparison DFT-B3LYP, the single-point energies have also been refined at the QCISD/6-31 ＋＋G（d,p） level to get more accurate energies using the MP2/6-31 ＋＋G（d,p） optimized geometries. The computational results indicate that the reaction involves two reaction channels which contain three reaction pathways to produce C3H3N2^- ＋CH2O and C4H5O^-＋N2, respectively. Channel 1 can be the main channel whose pathway 1 can also be the major pathway and pathway 3 is the major competition one with pathways 1 and 2. It is very reasonable and considerably consistent with the previous experimental results.

关 键 词：环丁烯负离子 反应机理 二阶微扰理论(MP2) 密度泛函理论(DFT) 

分 类 号：O643.12[理学—物理化学] TU834.84[理学—化学]