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氢转移反应HNCO+CH_x(x=1~3)的MP2和QCISD计算研究
引用本文:冀永强,冯文林,徐振峰,雷鸣,郝茂荣.氢转移反应HNCO+CH_x(x=1~3)的MP2和QCISD计算研究[J].化学学报,2002,60(7):1167-1172.
作者姓名:冀永强  冯文林  徐振峰  雷鸣  郝茂荣
作者单位:北京化工大学理学院,北京,100029
基金项目:国家教育部博士点基金 (No .9990 0 2 715 ),宁夏回族自治区教委基金资助项目
摘    要:在UMP2(FULL)/6-311(d,p)计算水平上,计算并讨论了碳氢自由基(CH_x) 和异氰酸(HNCO)发生氢转移反应位能面上驻点的结构和分子结构变化,并依据 UMP2的优化构型,进一步采用UQCISD(T)方法对反应途径上的驻点进行了单点能 量计算。研究指出,HNCO同CH_2,CH_3自由基反应时,氢转长期过程在分子间以新 的C-H键生成和旧的N-H键的断裂的协同方式进行,反应途径上均存在弱的氢键超分 子复合物;而HNCO和CH分子之间发生的氢转移反应机理是在反应剖面的反应物一边 生成一个较稳定的分子复合物HNJ(CH)CO,而后,在生成物一边又生成一个既有 热力学又有动力学稳定的复合物H_2CNCO。

关 键 词:异氰酸  游离基  构型  氢键  超分子结构
修稿时间:2001年10月17

MP2 and QCISD Study of Hydrogen Transfer Reaction Path of the Reaction HNCO with Carbon-Hydrogen Radicals CHx (x=1~3)
JI,Yong-Qiang FENG,Wen-Lin XU,Zhen-Feng LEI,Ming HAO,Mao-Rong.MP2 and QCISD Study of Hydrogen Transfer Reaction Path of the Reaction HNCO with Carbon-Hydrogen Radicals CHx (x=1~3)[J].Acta Chimica Sinica,2002,60(7):1167-1172.
Authors:JI  Yong-Qiang FENG  Wen-Lin XU  Zhen-Feng LEI  Ming HAO  Mao-Rong
Institution:College of Science, Beijing University of Chemical Technology. Beijing(100029)
Abstract:The reaction path of isocyanic acid (HNCO) with carbon-hydrogen radicals CH, CH 2 and CH 3 have been investigated by using UMP2 method at 6-311g(d, p) level. The geometries of the stationary points and the changes of molecular structure along the reaction path are discussed. Furthermore, the UQCISD(T, full) single-point energy calculations were performed on the geometries optimized at UMP2/6-311G(d, p) level. For the reactions of HNCO with CH 2 and HNCO with CH 3, we found that the formation of new C-H bond concerted with the break of old N-H bond along the IRC, and that there was a weak hydrogen-bond hyper-molecular complex on the reactant side for the both reactions. However, for the reaction of HNCO with CH there were two stable molecular complexes HN(CH)CO and H 2CNCO on the reactant side and the product side, respectively
Keywords:isocyanic acid  hydrogen abstraction reaction  MP2 and QCISD method  carbon-hydrogen radical
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