CH自由基和NO_2反应研究——Ⅱ.反应的动力学计算  

An Ab Initio Study on the Reaction of CH and NO_2——Ⅱ. Mechanism of the Reaction

作　　者：朱卡克[1] 王育彬[1] 黄明宝[2] 文振翼[1] 

机构地区：[1]西北大学现代物理研究所,西安710069 [2]中国科学技术大学研究生院,北京100039

出　　处：《化学学报》2000年第5期515-518,共4页Acta Chimica Sinica

基　　金：国家自然科学基金(29773035;29892162)资助项目

摘　　要：采用MP2(FULL)/6-31G(d)方法从动力学计算上探讨了CH自由基与NO_2反应的可能途径,找到了反应物,中间体及产物之间的能量通道和过渡态,报道了它们的构型、电子态及能量.并通过频率分析和IRC方法对所有的过渡态进行了验证.在此基础上求出了各步反应的活化能.在以前热力学研究的基础上,对于可能的反应通道进一步作了动力学分析,找到了反应主产物通道的分支比,与实验得到的分支比基本吻合.The reaction of methylidyne radical with molecule NO2 was studied theoretically by using MP2 (FULL)/6-31G(d) and QCISD(T)/6 - 31G(d). The reaction paths were found both for the formation of intermediates and the dissociation of some intermediates to form the products. The energies and structures of important intermediates and transition states were reported for the first time. The reaction path was followed from the transition state both to the reactant and the product direction by using the intrinsic reaction coordinate (IRC) method. By thermodynamic and mechanic analysis, the main reaction path channel was detected, the main products were found, and branching ratio was calculated, which was in good agreement with the experimental results.

关 键 词：CH自由基 反应焓变 二氧化氮 热力学计算 

分 类 号：O643.1[理学—物理化学]