OH+C_2H_2N←C_2H_3+NO→OH+C_2H_2N反应机理的密度泛函理论研究  

DFT theory study of reaction of OH+C_2H_2N←C_2H_3+NO→OH+C_2H_2N

作　　者：潘秀梅[1] 马继承[1] 傅强[1] 陈丽莉[1] 王荣顺[1] 

机构地区：[1]东北师范大学化学学院功能材料化学研究所,吉林长春130024

出　　处：《分子科学学报》2004年第3期29-35,共7页Journal of Molecular Science

基　　金：东北师范大学青年科学基金资助项目(111382)

摘　　要：　应用密度泛函理论研究了反应通道(a)C2H3+NO→CH3+NCO和(b)C2H3+NO→OH+C2H2N的反应机理.在B3LYP/6-31G(d)水平上优化了反应物、中间体、过滤态、产物的几何构型,通过频率分析确定了11个中间体和10个过渡态.所有的反应物、中间体、过渡态、产物都在CCSD/6-311++G(d,p)水平上进行了单点能较正.并讨论了反应的异构化过程.计算结果表明10是能量最低的中间体,比反应物的能量低308 479kJ/mol;过渡态1/3,2/5,3/4,4/8比反应物的能量高,其中3/4是能量最高的过渡态,比反应物的能量高91 894kJ/mol.通道(a)和(b)的理论放热值分别为111 059和96 619kJ/mol.The mechanisms of the reactions C_2H_3+NO→CH_3+NCO and C_2H_3+NO→OH+C_2H_2N have been studied by density functional theory.The geometries of reactants,intermediates,transition states and products have been optimized by B3LYP/6-31G(d) basis set.Single point energies were calculated at CCSD/6-311G++(d,p)level.Along the reaction path eleven intermediates and ten transition states were obtained through frequency analysis.The isomerization has been discussed.The results show that the tenth intermediate is the most steady one,whose energy is 308.479 kJ/mol lower than the reactants.The energy of the transition states 1/3,2/5,3/4,4/8 are higher than the reactants,among which 3/4 is the highest one.The path(a) and path(b)are exothermic with 111.059 and 96.619 (kJ/mol) exothermic value calculated respectively.

关 键 词：密度泛函理论 反应通道 反应机理 过渡态 乙烯自由基 异构化过程 

分 类 号：O623.121[理学—有机化学] O641.121[理学—化学]