CH自由基和NO_2反应研究——Ⅰ.反应的热力学计算  

An Ab Initio Study on the Reaction of CH and NO_2——Ⅰ. Thermodynamics of the Reaction

作　　者：朱卡克[1] 甘正汀[1] 苏克和[1] 王育彬[1] 文振翼[1] 

机构地区：[1]西北大学现代物理研究所,西安710069

出　　处：《化学学报》2000年第5期519-523,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(2977035)项目

摘　　要：探讨了CH自由基与NO_2反应的可能路径,通过计算确定了反应物,产物和稳定中间体的电子状态和平衡构型,并运用Gaussian-3方法和MRCISD方法对可能的反应路径进行了热力学计算.在多数情况下与实验值符合较好,对于个别与理论计算差别较大的实验值进行了评述.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 反应动力学 过渡态 活化能 二氧化氮 

分 类 号：O643.1[理学—物理化学]