甲基丁烯醇的光电离实验与理论研究

doi:10.7523/j.issn.2095-6134.2011.2.005

中国科学院大学学报 ›› 2011, Vol. 28 ›› Issue (2): 161-168.DOI: 10.7523/j.issn.2095-6134.2011.2.005

甲基丁烯醇的光电离实验与理论研究

孙月¹, 赵玉杰¹, 方文正¹, 孙金大¹, 单晓斌¹, 刘付轶¹, 盛六四¹, 王振亚^1,2

1. 中国科学技术大学国家同步辐射实验室, 核科学技术学院, 合肥 230029;
2. 中国科学院安徽光学精密机械研究所环境光谱学实验室, 合肥 230031

收稿日期:2010-05-20 修回日期:2010-06-10 发布日期:2011-03-15
基金资助:
Supported by the National Natural Science Foundation of China (10675112), 973 fund of Chinese Ministry of Science and Technology(2010CB934504), and the Knowledge Innovation Foundation of the Chinese Academy of Sciences(KJCX2-YW-N24)

Dissociative photoionization of methylbutenol: experimental and computational investigations

SUN Yue¹, ZHAO Yu-Jie¹, FANG Wen-Zheng¹, SUN Jin-Da¹, SHAN Xiao-Bin¹, LIU Fu-Yi¹, SHENG Liu-Si¹, WANG Zhen-Ya^1,2

1. National Synchrotron Radiation Laboratory, School of Nuclear Science and Technology, University of Science and Technology of China, Hefei 230029, China;
2. Laboratory of Environmental Spectroscopy, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China

Received:2010-05-20 Revised:2010-06-10 Published:2011-03-15
Supported by:
Supported by the National Natural Science Foundation of China (10675112), 973 fund of Chinese Ministry of Science and Technology(2010CB934504), and the Knowledge Innovation Foundation of the Chinese Academy of Sciences(KJCX2-YW-N24)

摘要/Abstract

摘要：

利用同步辐射光电离质谱的方法研究了甲基丁烯醇(C₅H₁₀O)在9.0~15.5eV的真空紫外光电离和光解离过程.通过测量光电离效率曲线,得到了C₅H₁₀O的电离能和主要碎片离子的出现势.通过对实验和计算结果的比较,分析了母体离子可能的光电离解离机理.母体离子的解离通道可以分为2类:由C₅H₁₀O⁺直接发生键断裂的解离和经由过渡态的解离.确定了C₄H⁺₅ 和C₃H⁺₅离子的过渡态和中间体,其反应势垒与实验解离能是符合的.

关键词: 甲基丁烯醇, 光电离和光解离, 同步辐射, G3B3计算

Abstract:

Vacuum ultraviolet (VUV) dissociative photoionization of methylbutenol (C₅H₁₀O) in 9.0~15.5 eV was investigated with photoionization mass spectrometry using synchrotron radiation (SR). The ionization energy of C₅H₁₀O and the appearance energies for the main fragment ions were determined with photoionization efficiency curves. The photodissociation mechanisms of methylbutenol were discussed based on comparison of our experimental results with those predicted by the quantum-chemical calculations. The dissociation channels may be divided into two types: the direct bond cleavage in C₅H₁₀O⁺ and the reactions involving transition states. Transition states and intermediates for C₄H⁺₅ and C₃H⁺₅ were determined, and the reaction barriers were in agreement with the experimental dissociation energies.

Key words: methylbutenol, photoionization and photodissociation, synchrotron radiation, G3B3 calculation

中图分类号:

O641

孙月, 赵玉杰, 方文正, 孙金大, 单晓斌, 刘付轶, 盛六四, 王振亚. 甲基丁烯醇的光电离实验与理论研究[J]. 中国科学院大学学报, 2011, 28(2): 161-168.

SUN Yue, ZHAO Yu-Jie, FANG Wen-Zheng, SUN Jin-Da, SHAN Xiao-Bin, LIU Fu-Yi, SHENG Liu-Si, WANG Zhen-Ya. Dissociative photoionization of methylbutenol: experimental and computational investigations[J]. , 2011, 28(2): 161-168.

参考文献

[1] SIDS initial assessment report for SIAM 4 . Ispra, Italy, UNEP Publications, 1995: 23-25.

[2] Baker B, Guenther A, Greenberg J,et al.Canopy fluxes of 2-methyl-3-buten-2-ol over a ponderosa pine forest by relaxed eddy accumulation: Field data and model comparison
[J]. Journal of Geophysical Research, 1999, 104: 26107-26114.

[3] Schade G W, Goldstein A H, Gray D W, et al. Canopy and leaf level 2-methyl-3-buten-2-ol fluxes from a ponderosa pine plantation
[J]. Atmospheric Environment, 2000, 34: 3535-3544.

[4] Chan W H, Galloway M M, Kwan A J, et al. Photooxidation of 2-Methyl-3-buten-2-ol (MBO) as a potential source of secondary organic aerosol
[J]. Environmental Science and Technology, 2009, 43: 4647-4652.

[5] Fantechi G, Jensen N R, Hjorth J, et al. Mechanistic studies of the atmospheric oxidation of methyl butenol by OH radicals, ozone and NO₃ radicals
[J]. Atmospheric Environment, 1998, 32: 3547-3566.

[6] Atkinson R, Arey J. Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review
[J]. Atmospheric Environment, 2003, 37: 197-219.

[7] Carrasco N, Doussin J F, O’Connor M, et al. Simulation chamber studies of the atmospheric oxidation of 2-Methyl-3-Buten-2-ol: reaction with Hydroxyl Radicals and Ozone under a variety of conditions
[J]. Journal of Atmospheric Chemistry, 2007, 56: 33-55.

[8] Steiner A L, Tonse S, Cohen R C, et al. Biogenic 2-methyl-3-buten-2-ol increases regional ozone and HO_<em>x sources
[J]. Geophysical Research Letters, 2007, 34:15806(1-6).

[9] Vajda J H, Harrison A G. Proton affinities of some olefinic carbonyl compounds and heats of formation of C_<em>nH_2n-1O⁺ ions
[J]. International Journal of Mass Spectrometry and Ion Physics, 1979, 30: 293-306.

[10] Zwinselman J J, Nibbering N M, Middlemiss N E, et al. A field Ionization kinetics and metastable ion study of the fragmentation of some pentenols
[J]. Journal of Geophysical Research, 1981, 38: 163-179.

[11] Rudich Y, Talukdar R, Burkholder J B, et al. Reaction of methylbutenol with Hydroxyl radical: mechanism and atmospheric implications
[J]. Journal of Physical Chemistry, 1995, 99: 12188-12194.

[12] Curtiss L A, Raghavachari K, Redfern P C, et al. Gaussian-3 (G3) theory for molecules containing first and second-row atoms
[J]. Journal of Chemical Physics, 1998, 109: 7764-7776.

[13] Baboul A G, Curtiss L A, Redfern P C, et al. Gaussian-3 theory using density functional geometries and zero-point energies
[J]. Journal of Chemical Physics, 1999, 110: 7650-7657.

[14] Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 03, Revision C.01 . .http://www.psc.edu/general/software/packages/gaussian/G03C01_release_notes.html. Gaussian: Wallingford,CT, 2004.

[15] Wang S S, Kong R H, Shan X B, et al. Performance of the atomic and molecular physics beamline at the National Synchrotron Radiation Laboratory
[J]. Journal of Synchrotron Radiation, 2006, 13: 415-420.

[16] Kong R H, Shan X B, Wang S S, et al. Experimental and theoretical study of Ne…CO cluster
[J]. Journal of Electron Spectroscopy and Related Phenomena, 2007, 160: 49-53.

[17] Levy M, Yang W, Parr R G. A new functional with homogeneous coordinate scaling in density functional theory
[J]. Journal of Chemical Physics, 1985, 83: 2334-2336.

[18] Kohn W, Becke A D, Parr R G. Density functional theory of electronic structure
[J].Journal of Physical Chemistry, 1996, 100: 12974-12980.

[19] Chiang S Y, Bahou M, Sankaran K, et al. Dissociative photoionization of CH₂Cl₂ and enthalpy of formation of CHCl⁺: experiments and calculations
[J]. Journal of Chemical Physics, 2003, 62: 118-125.

[20] Wang Z Y, Hao L Q, Zhou S K, et al. VUV dissociative photoionization of CHF₂Cl
[J]. Journal of Molecular Structure, 2007, 826: 192-197.

[21] NIST. 3-Buten-2-01,2-methyl-. .http://webbook.nist.gov/cgi/cbook.cgi?ID=C115184&Units=SI&Mask=2A0.

甲基丁烯醇的光电离实验与理论研究

Dissociative photoionization of methylbutenol: experimental and computational investigations

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