Photoionization/Photodissociation Mechanism of Allyl Chloride with a Femtosecond Laser Pulse

Abstract

Abstract: The photoionization/photodissociation mechanism of allyl chloride has been studied by a 50-fs laser pulse at 200 nm, 400 nm and 800 nm. With the mass spectra and laser power index that record at three different wavelengths, the dependence of quantum yield on the wavelength is analyzed. It is found that the parent ion (C3H5Cl+) comes from directly non-resonance ionization with 200 nm femtosecond pulse, while the daughter ions are from dissociative ionization of C3H5Cl+. At 400 nm, some molecules are excited to the high Rydberg state and C3H5 radicals are generated by direct dissociation. The enhancement of C3H5+ signal is observed since multi-photon ionization of C3H5 increases the population of C3H5+. At 800 nm, nσ* states and some Rydberg states are both populated. The further increased population of C3H5 leading to an increase of C3H5+. On the other hand, the wavelength dependence of C3H4+ yield is less pronounced, since it comes from dissociative ionization of C3H5+ and C3H5Cl+.

Key words: spectroscopy; mass spectrum; femtosecond pulse; allyl chloride; photoionization; photodossiciation

CLC Number:

O433
O561

SHEN Huan, ZHANG Bing. Photoionization/Photodissociation Mechanism of Allyl Chloride with a Femtosecond Laser Pulse[J]. J4, 2016, 33(2): 129-134.

References

[1] Randy D Buff, Albert C Parr, Andrew J Jason. The photoionization of allyl chloride from onset to 20eV [J]. International Journal of Mass Spectrometry and ion physics, 1981, 40():31-34
[2] C Traeger John. A study of the allyl cation thermochemistry by photoionzation mass spectrometry [J]. International Journal of Mass Spectrometry and ion processes, 1984, 58(): 259-271
[3] Ankur Saha, Hari P Upadhyaya, Awadhesh Kumar. Dynamics of C-Cl bond fission in photodissociation of 2-furoyl chloride at 235 nm [J]. Chemical Physics, 2012, 402(): 74-82
[4] Shen Huan, Hua Linqiang, Cao Zhenzhou, Bing Zhang. C-Br bond fission dynamics in ultraviolet photodissociation of propargyl bromide [J]. Optics Communications, 2009, 282(3): 287-291
[5] Ji Lei, Tang Ying, Zhu Rongshu, Wei Zhengrong, Zhang Bing. Photodissociation dynamics of allyl bromide at 234, 265, and 267 nm [J]. Journal of Chemical Physics, 2006, 125(16): 164307.1-8
[6] Fan H, Pratt S T.Determination of spin-orbit branching fractions in the photodissociation of halogenated hydrocarbons [J]. Journal of Physical Chemistry A, 2007, 111(19): 3901-3906
[7] Myers T L, Kitchen D C, Hu B, Butler L J. Investigating Conformation Dependence and Non-Adiabatic Effects in the Photodissociation of Allyl Chloride at 193 nm [J]. Journal of chemical physics, 1996, 104(14):5446-5456
[8] Morton M L, Butler L J, Stephenson T A. C-Cl bond fission, HCl elimination, and secondary radical decomposition in the 193 nm photodissociation of allyl chloride [J]. Journal of Chemical Physics, 2002, 116(7): 2763-2775
[9] Liu Y, Bulter L J. C-Cl Bond Fission Dynamics and Angular Momentum Recoupling in the 235 nm Photodissociation of Allyl Chloride [J]. Journal of Chemical Physics,2004, 121(22): 11016-11022
[10] Fischer I, Schutler T, Deyerl H J, Elhanine M, Alcaraz C. Photoionization and dissociative photoionization of the allyl radical, C3H5 [J]. International Journal of Mass Spectrometry, 2007, 261(2-3): 227–233
[11] Gilbert T, Pfab R, Fischer I, Chen P. The zero kinetic energy photoelectron spectrum of the propargyl radical, C3H3 [J]. Journal of Chemical Physics, 2000, 112(6): 2575-2578
[12] Gilbert T, Fischer I, and Chen P. Zero kinetic energy photoelectron spectra of the allyl radical, C3H5 [J]. Journal of Chemical Physics, 2000, 113(2): 561-566
[13]Jin Bae Yong, Lee Mina, Kim Soo Myung. One-photon mass-analyzed threshold ionization spectroscopy of 2-chloropropene,2-C3H5CL and its vibrational assignment based on the density-functional theory calculations [J]. Journal of Chemical Physics, 2005, 123(4): 044306.1-8
[14] Fu Q, Seier F, Gayen S K, Alfano R R. High-average-power kilohertz-repetition-rate sub-100-fs Ti:sapphire amplifier system [J]. Optics Letters, 1997, 22(10): 712-714
[15] Wu ChengYin, Gong QiHuang. Ionization of molecules irradiated by an intense femtosecond laser field [J]. Physics(In Chinese), 2006, 35(08): 666-672
[16] Hua Linqiang, Shen Huan, Hu Changjin, Zhang Bing. Photoelectron imaging of atomic chlorine and bromine following photolysis of CH2BrCl [J]. Journal of Chemical Physics, 2008, 129(24): 244308.1-7
[17] Li WenJuan, Zhou LiuZhu, Kong ZhenZhen, Liu DongMei, Zhang ShuDong, Kong HeXiang. Study on multiphoton ionization dissociation processes of ethyl iodide at 800 nm laser radiation [J]. Journal of atomic and molecular physics(In Chinese), 2012, 29(6):1040-1044
[18]Shen Huan, Chen JianJun, Hua Linqiang, Zhang Bing. Photodissociation Dynamics of Allyl Chloride at 200 and 266 nm Studied by Time-resolved Mass Spectrometry and Photoelectron Imaging [J]. Journal of Physical Chemistry A, 2014, 118(25): 4444-4450
[19]Worrell C W. The photoelectron and absorption spectra of allyl halides [J]. Journal of Electron Spectroscopy and Related Phenomema, 1974, 3(): 359-367
[20] Farmanara P, Steinkellner O, Wick M T, Wittmann M, Korn G, Stert ., Radloff W. Ultrafast internal conversion and photodissociation of molecules excited by femtosecond 155 nm laser pulses [J]. Journal of Chemical Physics, 1999, 111(14): 6264-6270