异戊二烯与OH自由基反应机理及其振动光谱研究

J4 ›› 2013, Vol. 30 ›› Issue (6): 658-664.

异戊二烯与OH自由基反应机理及其振动光谱研究

刘宪云^1,2,钱忠健¹,王旭东¹,王振亚²,张为俊²

1 常州大学数理学院,江苏常州 213164;
2 中国科学院安徽光学精密机械研究所大气物理化学研究室,安徽合肥 230031

收稿日期:2013-03-19 修回日期:2013-04-22 出版日期:2013-11-28 发布日期:2013-11-13
作者简介:刘宪云 ( 1977 - ), 女, 山东临沂人, 博士,主要从事环境光谱学方面的研究。 E-mail:xyliu@cczu.edu.cn
基金资助:
常州大学科研启动基金(ZMF1102073)、常州市科技项目(CJ20120031)、教育部第46批留学回国人员科研启动基金(2013z0031)

Reaction mechanism and vibrational spectroscopy of OH-initiated isoprene photooxidation

LIU Xian-yun^1,2, QIAN Zhong-jian¹,WANG Xu-dong¹,WANG Zhen-ya², ZHANG Wei-jun²

1 School of Mathematics and Physics, Changzhou University,Changzhou 213164,China;
2 Laboratory of Atmospheric Physics and Chemistry, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of
Sciences,Hefei 230031,China

Received:2013-03-19 Revised:2013-04-22 Published:2013-11-28 Online:2013-11-13

摘要/Abstract

摘要：

采用红外傅里叶变换光谱仪测量了异戊二烯与羟基反应产物的红外光谱,并结合量子化学理论密度泛函方法对异戊二烯与羟基自由基的反应机理进行了理论研究。使用密度泛函B3LYP/6-31G(d,p)方法计算了异戊二烯羟基加成反应中每个反应物和产物的频率,实验与理论结果符合的很好。研究发现了破坏羟基进攻异戊二烯的反应通道,并从机理上探讨了阻断该关键反应通道的方法。

关键词: 光谱学, 振动光谱, 量子化学, 异戊二烯, 生物源挥发性有机污染物

Abstract:

Fourier transform infrared spectroscopy (FTIR) was used to measure the spectroscopic information of isoprene. Using Gaussian
03 program under density functional theory (DFT), the reaction mechanism of OH $^-$ isoprene adducts were studies with $ab initio$ methods at the
B3LYP/6-31G(d,p) level of theory for optimized geomethies and frequency calculations. Results show that the experimental results
agreed well with the theoretical values. The pathways involved in the reaction between OH $^-$ and isoprene were found and the methods to
block this key reaction pathway in principle were discussed.

Key words: spectroscopy, vibrational spectroscopy, quantum chemistry, isoprene, biogenic volatile
organic compounds

中图分类号:

O644

刘宪云,钱忠健,王旭东,王振亚,张为俊. 异戊二烯与OH自由基反应机理及其振动光谱研究[J]. J4, 2013, 30(6): 658-664.

LIU Xian-yun,QIAN Zhong-jian,WANG Xu-dong,WANG Zhen-ya,ZHANG Wei-jun. Reaction mechanism and vibrational spectroscopy of OH-initiated isoprene photooxidation[J]. J4, 2013, 30(6): 658-664.

参考文献

[1] Brana P, Sordo J A. Mechanistic aspects of the abstraction of an allylic hydrogen in the chlorine atom reaction with 2-Methyl-1,3-Butadiene (Isoprene) [J]. J. Am. Chem. Soc., 2001, 123: 10348-10353. [2] Hohenberg P, Kohn W. Inhomogeneous electron gas [J]. Phys. Rev. 1964, 136: B864-B871. [3] Kohn W, Sham L J. Self-consistent equations including exchange and correlation effects [J]. Phys. Rev. 1965, 140: A1133-A1138. [4] Slater J C. Quantum Theory of Molecular and Solids. Vol. 4: The Self-Consistent Field for Molecular and Solids [M]. McGraw-Hill: New York, 1974. 1-200. [5] Parr R G, Yang W. Density-Functional Theory of Atoms and Molecules [M]. Oxford Univ. Press: Oxford, 1989. 1-333. [6] Becke A D. Density-functional thermochemistry. I. The effect of the exchange-only gradient correction [J]. 1992, 96: 2155-2160. [7] Becke A D. Density-functional thermochemistry. II. The effect of the Perdew–Wang generalized-gradient correlation correction. [J]. Journal of Chemical Physics, 1992, 97: 9173-9177. [8] Nguyen M T, Creve S, Vanquickenborne L G. Properties of phosphorus compounds by density functional theory: CH3P species as a test case. [J]. Journal of Chemical Physics, 1998, 105: 1922-1932. [9] Gaussian 03, Revision C.01, Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian, Inc., Wallingford CT, 2004. [10] Hao L Q, Wang Z Y, Huang M Q, et al. Size distribution of the secondary organic aerosol particles from the photooxidation of toluene [J]. J. Environ. Sci., 2005, 17(6): 912—916. [11] Liu X Y, Zhang W J, Huang M Q, et al. Effect of illumination intensity and light application time on secondary organic aerosol (SOA) formation from the photooxidation of α-pinene [J]. J. Environ. Sci., 2009, 21(4): 447—451. [12] Atkinson R, Carter W P L, Winer A M, et al. An experimental protocol for the determination or OH radical rate constants with organics using methyl nitrite photolysis as an OH radical source [J]. J Air Pollution Control Association, 1981, 31(10): 1090—1092. [13] Stevens P S, Seymour E, Li Z. Theoretical and experimental studies of the reaction of OH with isoprene [J]. J. Phys. Chem. A, 2000, 104: 5989-5997. [14] Diaz-Acosta I, Alvarez-Idaboy J R, VivierBunge A. Mechanism of the OH-propene-O2 reaction: An ab initio study [J]. Int. J. Chem. Kinet., 1999, 31: 29-36. [15] Alvarez-Idaboy J R, Mora-Diez N, Vivier-Bunge A. A quantum chemical and classical transition state theory explanation of negative activation energies in OH addition to substituted ethenes [J]. J. Am. Chem. Soc., 2000, 122: 3715-3720. [16] Uc V H, García-Cruz I, Hernández-Laguna A, Vivier-Bunge A. New channels in the reaction mechanisms of the atmospheric oxidation of toluene [J]. J. Phys. Chem. A, 2000, 104(33): 7847-7855. [17] Suh I, Zhang D, Zhang R, Molina L T, Molina M J. Theoretical study of OH addition reaction to toluene [J]. Chem. Phys. Lett, 2002, 363: 454-462. [18] Liu Xianyun, Zhang Weijun, Huang Mingqiang, Wang Zhenya. FTIR Spectra of Isoprene and its Photooxidation Products [J]. Journal of Infrared and Millimeter Waves(红外与毫米波学报), 2010, 29(2):114-116 (in Chinese). 刘宪云，张为俊，黄明强，王振亚. 异戊二烯及其光氧化产物的傅里叶变换红外光谱研究 [J].红外与毫米波学报，2010, 29(2):114-116. [19] Lu Yongquan, Deng Zhenhua. The analysis of infrared spectrum（实用红外光谱解析）, [M]. Beijing: Electronic Industry Press, 1989, 20-35 (in Chinese). 卢涌泉, 邓振华. 实用红外光谱解析. 北京：电子工业出版社，1989，20—35.

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