CH_3NO异构体及异构化反应机理的量子化学研究  

Quantum Chemical Study on the Isomers and Isomerization Reaction Mechanism of CH_3NO

作　　者：杨丽娟[1,2] 李晓艳[3] 曾艳丽[3] 郑世钧[3] 孟令鹏[3] 赵毅[1] 

机构地区：[1]华北电力大学环境科学与工程学院,保定071003 [2]华北电力大学科技学院,保定071003 [3]河北师范大学化学与材料科学学院,石家庄050016

出　　处：《化学学报》2011年第5期577-584,共8页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.20973053;20771033;20801017);河北省自然科学基金(Nos.B2008000141;B2008000138;B2010000371);河北省教育厅基金(No.2009137);华北电力大学青年教师科研基金(No.200811033);河北师范大学科研基金(Nos.L2008B06;L2009Y06)资助项目

摘　　要：在CCSD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p)水平上对CH3NO的异构体及各异构化反应机理进行了详细的理论研究.包括CH3NO共找到了23种异构体,这23种异构体间通过24个过渡态相互转化.用振动频率分析证实了过渡态的真实性,内禀反应坐标跟踪(IRC)计算验证了过渡态与各异构体的连接关系.计算结果表明,在CH3NO的各种异构体中,分子骨架中存在N—C—O结构是最稳定的,而C—O—N,C—N—O结构能量最高,不稳定.异构体间的异构化反应主要通过化学键的旋转,H迁移,C,N,O骨架的重组及包含上述两种机理的混合型机理等4种方式完成.The structures of CH3NO isomers and their isomerization have been investigated at CCSD（T）/ 6-311 ＋＋ G（d,p）//B3LYP/6-311＋＋GG（d,p） level. 23 isomers including CH3NO were found and they were linked by 24 transition states. The characterizations of the transition states are confirmed by vibration analysis. The intrinsic reaction coordinates （IRC） have been traced according to Fukui＇s theory and the connecting relationship of the transition states with the reactants and products was confirmed. The calculated results show that the isomers with N-C-O structure are the most stable, while those with C-O-N and C-N-O structures are not stable because of their high energies. The isomers transform to each other by the rotation of the chemical bond, the transfer of H atom, the reaction mechanism of above-mentioned. reorganization of C, N and O skeleton and the mixed typereaction mechanism of above-mentioned.

关 键 词：CH3NO 异构化反应 过渡态 反应机理 

分 类 号：O643.12[理学—物理化学]