XNO_2(X=F,Cl,Br,I)异构体的结构与异构化研究  

A DFT Study on the Structure and Isomerizerization of Nitryl Halogenides

作　　者：崔小英[1] 秦晓芳[1] 武海顺[1] 

机构地区：[1]山西师范大学化学与材料科学学院,山西临汾041004

出　　处：《山西师范大学学报（自然科学版）》2005年第2期49-54,共6页Journal of Shanxi Normal University(Natural Science Edition)

基　　金：教育部骨干教师资助计划项目;山西省自然科学基金(20011015)

摘　　要：通过密度泛函理论(DFT)的B3LYP方法进行优化计算,得到了卤素氮氧化物XNO2(X=F,Cl,Br,I)三种异构体的平衡几何构型,预测了各异构体的相对稳定性.其中,异构体XNO2的能量最低,其次是cis-XONO.同时讨论了它们的互变异构反应及其相互转化的活化能垒,得到了过渡态的结构.在B3LYP和QCISD(T)计算水平上,确定了各异构体中X-N与X-O键的解离能.The density functional theory studies with B3LYP method on the equilibrium geometries and harmonic vibrational frequencies of nitryl halogenides XNO_2 and XONO(X=F,Cl,Br,I), have been reported in the present paper. The calculation results suggest that the XNO_2 isomers are more stable than their branched structures thermodynamically. The activation energies for the unimolecular isomerization were predicted at the same level, and the transition states were also obtained. Dissociation energy of the X-N bond in XNO_2 and the X-O bond in XONO(X=F,Cl,Br,I) have been estimated at the B3LYP/6-311G* and QCISD(T)/cc-pvTZ levels.

关 键 词：异构体 密度泛函理论(DFT) CL BR 结构 异构化 B3LYP方法 平衡几何构型 互变异构反应 相对稳定性 优化计算 氮氧化物 相互转化 过渡态 解离能 卤素 能垒 

分 类 号：O613.71[理学—无机化学] O641.121[理学—化学]