Reaction mechanism and vibrational spectroscopy of OH-initiated isoprene photooxidation

Abstract

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

CLC Number:

O644

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.

References

[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.