FC(O)O2的结构及其自由基与NO反应的微观机理研究

周翔; 张萱; 刘爱芬; 曾祥华

doi:10.7498/aps.59.5128

摘要

用密度泛函理论(DFT)和哈特里-福克(HF)从头计算方法和半经验势方法等研究了FC(O)O2 的结构和振动性质.在DFT中采用B3LYP方法,在6-311G(d)基组上对FC(O)O2自由基与NO反应的微观过程进行了分析.首先给出了各反应物、中间体、过渡态和生成物的几何构型,然后计算了它们的能量和频率,通过频谱分析得到反应的中间体和过渡态信息,即FC(O)O2与NO反应为多反应通道,势垒高度和反应速度给出主要通道是FC(O)O2

关键词:

密度泛函理论 /
FC(O)O2 /
NO /
反应机理

Abstract

Density functional theory was performed to study the reaction mechanism of the reaction of FC(O)O2 with NO. The geometric configurations of reactants, intermediates, transition states and products were optimized by B3LYP method at 6-311G(d) level. The energies of stationary points along the pathway were also calculated. Intermediates and transition states were confirmed by the results of vibrational analysis. From the results of the mechanism of the reaction of FC(O)O2 with NO, we found that the reaction of FC(O)O2+NO has four pathways and several steps. Comparing the four pathways activation energies, we can find that the pathway FC(O)O2+NO→bM→bT→FC(O)O+NO2 is the main reaction pathway and the main products are FC(O)O radical and NO2, which is in good agreement with the result reported in the literature.

Keywords:

作者及机构信息

1.
扬州大学物理科学与技术学院,扬州 225002

基金项目: 江苏省科技计划(批准号: BG2007026)资助的课题.

Authors and contacts

1.
College of Physics Science and Technology, Yangzhou University, Yangzhou 225002, China

参考文献

[1]	Cicerone J R 1987Science 237 35
[2]	7349 (in Chinese) [赵江、曾祥华、崔磊、徐秀莲 2008 57 7349]
[3]	Maricq M M, Szente J J, Li Z, Francisco J S 1993 J. Chem. Phys. 98 784
[4]	Francisco J S, Goldstein A N, Li Z, Zhao Y, Williams I H 1990 J. Phys. Chem. 94 4791
[5]	Dibble T S, Francisco J S 1994 J. Phys. Chem. 98 10374
[6]	Maricq M M, Szente J J, Dibble T S, Francisco J S 1994 J. Phys. Chem. 98 12294
[7]	Dibble T S, Francisco J S 1994 J. Phys. Chem. 98 1694
[8]	Dibble T S, Francisco J S 1994 J. Phys. Chem. 99 5010
[9]	Dibble T S, Francisco J S, Deeth R J, Hand M R, Williams I H 1994 J. Chem. Phys. 100 459
[10]	Joseph S, Francisco J S 1996 Acc. Chem. Res. 29 391
[11]	Zhao J, Zeng X H, Cui L, Xu X L 2008 Acta Phys. Sin. 57
[12]	Hohenberg P, Kohn W 1964 Phys. Rev. B 136 864
[13]	Kohn W, Sham L J 1965 Phys. Rev. A 140 1133
[14]	Wei Y Y, Li J 2004 The Conspectus of Chemical Reaction Mechanism (Beijing: Science Press) (in Chinese)
[15]	Zhao X S 2004 The Conspectus of Chemical Reaction Theory (Beijing: Peking University Press) (in Chinese) [赵新生 2003 化学反应理论导论 (北京:北京大学出版社)]
[16]	Zhang J S, Meng Q X, Li M 2005 Acta Chimica Sinica 63 686(in Chinese)[张金生、孟庆喜、李明 2005 化学学报 63 686]

施引文献

[1]	Cicerone J R 1987Science 237 35
[2]	7349 (in Chinese) [赵江、曾祥华、崔磊、徐秀莲 2008 57 7349]
[3]	Maricq M M, Szente J J, Li Z, Francisco J S 1993 J. Chem. Phys. 98 784
[4]	Francisco J S, Goldstein A N, Li Z, Zhao Y, Williams I H 1990 J. Phys. Chem. 94 4791
[5]	Dibble T S, Francisco J S 1994 J. Phys. Chem. 98 10374
[6]	Maricq M M, Szente J J, Dibble T S, Francisco J S 1994 J. Phys. Chem. 98 12294
[7]	Dibble T S, Francisco J S 1994 J. Phys. Chem. 98 1694
[8]	Dibble T S, Francisco J S 1994 J. Phys. Chem. 99 5010
[9]	Dibble T S, Francisco J S, Deeth R J, Hand M R, Williams I H 1994 J. Chem. Phys. 100 459
[10]	Joseph S, Francisco J S 1996 Acc. Chem. Res. 29 391
[11]	Zhao J, Zeng X H, Cui L, Xu X L 2008 Acta Phys. Sin. 57
[12]	Hohenberg P, Kohn W 1964 Phys. Rev. B 136 864
[13]	Kohn W, Sham L J 1965 Phys. Rev. A 140 1133
[14]	Wei Y Y, Li J 2004 The Conspectus of Chemical Reaction Mechanism (Beijing: Science Press) (in Chinese)
[15]	Zhao X S 2004 The Conspectus of Chemical Reaction Theory (Beijing: Peking University Press) (in Chinese) [赵新生 2003 化学反应理论导论 (北京:北京大学出版社)]
[16]	Zhang J S, Meng Q X, Li M 2005 Acta Chimica Sinica 63 686(in Chinese)[张金生、孟庆喜、李明 2005 化学学报 63 686]

姓名
邮箱
手机号码
标题
留言内容
验证码

搜索

留言板