甲胺分子的紫外光解离动力学实验研究
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摘要
在280—287.5 nm区域内,通过实验测定共振增强多光子电离-时间飞行质谱、碎片离子的分质量激发谱以及光强指数等对甲胺分子的光解离通道进行了研究.实验结果证实甲胺分子在单光子能量范围内存在一个电子排斥态,主要的光解离过程为甲胺分子共振吸收1个光子到达该电子排斥态后解离成中性碎片,然后是中性碎片经多光子共振电离形成碎片离子和碎片离子的进一步解离.
Methyl amine is the simplest alkyl amine. It is a typical molecule in the field of surface physicochemistry. The basic properties of the structure and reaction activity of this molecule are essential to understand its role in many chemical reactions. Its energy state and ionic structure, ionization dissociation channel and competition have aroused the interest of astronomical and physicochemical researchers. In order to further understand the mechanism of multiphoton dissociation and ionization of methylamine in this energy region, the photodissociation channels of methylamine are studied based on the measured resonance enhanced multiphoton ionization-time-of-flight mass spectrum(TOFMS),mass-selected excitation spectra of the ionized fragment, and laser power index of each ion in a range of 280-287.5 nm.The multiphoton ionization TOFMS of methylamine molecule is obtained at the excited laser wavelength of 283 nm.After calibration, the weaker ion peaks correspond to the C~+,CH~+,CH_2~+, CH_3~+,NH_2~+, NH_3~+,CN~+,CH_2 NH~+(CHNH_2~+,CH_3 N~+), CH3 NH_2~+;the mass-to-charge ratio of stronger peaks except H~+ ions are 27, 28 and 30, respectively, and the mass-to-charge ratio of 28 and 30 belong to CHNH~+, CH2 NH_2~+ after analysis and discussion. Combining with the mass separation excitation spectra of the parent ions, it is concluded that there is a repulsive electronic state in the single photon energy. The main dissociation channel is the resonant photodissociation of the parent molecule in the repulsive state produced by one photoabsorption, followed by the photoionization of the fragment through the(1+1) multiphoton process and the further photodissociation of the ionized fragment.
Methyl amine is the simplest alkyl amine. It is a typical molecule in the field of surface physicochemistry. The basic properties of the structure and reaction activity of this molecule are essential to understand its role in many chemical reactions. Its energy state and ionic structure, ionization dissociation channel and competition have aroused the interest of astronomical and physicochemical researchers. In order to further understand the mechanism of multiphoton dissociation and ionization of methylamine in this energy region, the photodissociation channels of methylamine are studied based on the measured resonance enhanced multiphoton ionization-time-of-flight mass spectrum(TOFMS),mass-selected excitation spectra of the ionized fragment, and laser power index of each ion in a range of 280-287.5 nm.The multiphoton ionization TOFMS of methylamine molecule is obtained at the excited laser wavelength of 283 nm.After calibration, the weaker ion peaks correspond to the C~+,CH~+,CH_2~+, CH_3~+,NH_2~+, NH_3~+,CN~+,CH_2 NH~+(CHNH_2~+,CH_3 N~+), CH3 NH_2~+;the mass-to-charge ratio of stronger peaks except H~+ ions are 27, 28 and 30, respectively, and the mass-to-charge ratio of 28 and 30 belong to CHNH~+, CH2 NH_2~+ after analysis and discussion. Combining with the mass separation excitation spectra of the parent ions, it is concluded that there is a repulsive electronic state in the single photon energy. The main dissociation channel is the resonant photodissociation of the parent molecule in the repulsive state produced by one photoabsorption, followed by the photoionization of the fragment through the(1+1) multiphoton process and the further photodissociation of the ionized fragment.
引文
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[19]Onitsuka Y, Yamasaki K, Goto H, Kohguchi H 2016 J.Phys. Chem. A 120 8584
[20]Epshtein M, Portnova A, Bar I 2015 Phys. Chem. Chem.Phys.17 19607
[21]Li X, Vidal C R 1995 J. Chem. Phys. 102 9167
[22]Donchi K F, Rumpf B A, Willet G D 1988 J. Am. Chem.Soc. 110 347
[2]Taylor D P, Bernstein E R 1995 J. Chem. Phys. 10310453
[3]James O T, Katherine E L, Craig M 2014 J. Phys. Chem.A 118 9844
[4]Tossell J A, Lederman S M, Moore J H, Coplan M A,Chornay D A 1984 J. Am. Chem. Soc. 106 976
[5]Xiao H Y, Satoshi M, Keiji M 2013 J. Phys. Chem. A117 5757
[6]James O T, Katherine E L, Craig M 2012 J. Phys. Chem.Lett. 3 1341
[7]Long C L, William K B 1982 J. Appl. Phys. 53 203
[8]Michael J V, Noyes W A 1963 J. Am, Chem. Soc. 851228
[9]Waschewsky G C,Kitchen D C, Browning P W, Butler L J 1995 J. Phys. Chem. 99 2635
[10]Reed C L, Kono M, Ashfold M N R 1996 J. Chem. Soc.Faraday Trans. 92 4897
[11]Ashfold M N R, Dixon R N, Kono M, Mordaunt D H,Reed C L 1997 Philos. Trans. R. Soc, London Ser. A355 1659
[12]Dunn K M, Morokuma K 1996 J. Phys. Chem. 100 123
[13]Sun J B, Kyo W C, Young S C, Sang K K 2002 J. Chem.Phys.117 10057
[14]Baek S J, Choi K W, Choi Y S 2003 J. Chem. Phys.118 11026
[15]Baek S J, Choi K W, Choi Y S, Kim S K 2003 J. Chem.Phys. 118 11040
[16]Liu X J, Zhang B, Fang L, Guo W Y, Zhou J G, Cai J Y, Lu Y Q, Zhou S K 1996 Acta Phys.-Chim. 12 981(in Chinese)[柳晓军,张冰,方黎,郭文跃,周金刚,蔡继业,路轶群,周世康1996物理化学学报12 981]
[17]Fang L, Zhang B, Liu X J, Guo W Y, Wei J, Cai J Y1997 Acta Opt.Sin. 17 1638.(in Chinese)[方黎,张冰,柳晓军,郭文跃,魏杰,蔡继业1997光学学报17 1638]
[18]Hu Z F, Wang Z Y, Kong X L, Zhang X Y, Li H Y, Zhou S K 2002 Acta Phys. 51 235(in Chinese)[胡正发,王振亚,孔祥蕾,张先义,李海洋,周士康2002物理学报51235]
[19]Onitsuka Y, Yamasaki K, Goto H, Kohguchi H 2016 J.Phys. Chem. A 120 8584
[20]Epshtein M, Portnova A, Bar I 2015 Phys. Chem. Chem.Phys.17 19607
[21]Li X, Vidal C R 1995 J. Chem. Phys. 102 9167
[22]Donchi K F, Rumpf B A, Willet G D 1988 J. Am. Chem.Soc. 110 347