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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (3): 325-334. 上一篇    下一篇

研究论文

气相中环丁烯负离子与N2O反应机理的理论研究

耿志远*，梁俊玺，王永成，韩彦霞，闫盆吉   

  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)
  • 投稿日期:2007-04-26 修回日期:2007-09-05 发布日期:2008-02-14
  • 通讯作者: 耿志远

Theoretical Study Reaction of C4H5- with N2O in Gas Phase

GENG Zhi-Yuan*; LIANG Jun-Xi; WANG Yong-Cheng; HAN Yan-Xia ;YAN Peng-Ji   

  1. (Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070)
  • Received:2007-04-26 Revised:2007-09-05 Published:2008-02-14
  • Contact: GENG Zhi-Yuan

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783

被引次数

4

采用B3LYP 和MP2两种计算方法，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。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、2的竞争反应。理论计算结果与实验预测基本一致。

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)

The mechanism for the ion-molecule reaction of cyclobutene anion with nitrous oxide have been characterized in detail, Based on 6-31++G(d,p) basis set,using the Second-order Møller-Plesset perturbation theory (MP2) and comparison DFT-B3LYP,We have presented a theoretical rationalization of the previous experimental results on the reaction of C4H5- with N2O. The external N-atom was attacked by C4H5-, It is very reasonable and considerably consistent with the previous experimental results.

Key words: cyclobutene anion, reaction mechanism, second-order Mø, ller-Plesset perturbation theory, density functional theory