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Photodissociation Dynamics of Alkyl Nitrites at 266 and 355 nm: The OH Product Channel
Yue, Xian-Fang; Sun, Ju-Long; Yin, Hong-Ming; Wei, Qiang; Han, Ke-Li; Han KL(韩克利)
刊名JOURNAL OF PHYSICAL CHEMISTRY A
2009-04-09
DOI10.1021/jp810731d
113期:14页:3303-3310
收录类别SCI
文章类型Article
部门归属11
项目归属1101
产权排名1;1
WOS标题词Science & Technology ; Physical Sciences
类目[WOS]Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
研究领域[WOS]Chemistry ; Physics
关键词[WOS]TERT-BUTYL NITRITE ; POTENTIAL-ENERGY SURFACES ; TRANS-METHYL NITRITE ; JET-COOLED METHYL ; MOLECULAR-BEAM ; S-2 STATE ; NO FRAGMENT ; LASER PHOTOLYSIS ; CH3ONO ; SPECTRA
英文摘要Photodissociation of methyl nitrite and n-butyl nitrite at 266 and 355 nm has been investigated in the gas phase at room temperature. OH photoproducts were observed, and their internal state distributions were measured by the one-photon laser-induced fluorescence (LIF) technique. It was found that the nascent OH from the 266 nm photolysis of methyl nitrite was vibrationally cold, and its rotational state distribution conformed to a Boltzmann behavior with a rotational temperature of T(rot) = 2200 +/- 150 K. In contrast, the nascent OH from the 266 nm photolysis of n-butyl nitrite was found to be vibrationally excited, and the measured relative population of upsilon '' = 0: 1 was 0.78: 0.22. The rotational state distribution of the OH upsilon '' = 1 state conformed to Boltzmann behavior, with a rotational temperature of T(rot) = 1462 +/- 120 K. However, a simple Boltzmann distribution was not found for the OH upsilon '' = 0 state. In the photolysis of n-butyl nitrite at 355 nm, the OH fragment was found to be vibrationally cold and its rotational state distribution showed non-Boltzmann behavior. A photodissociation mechanism involving an intramolecular hydrogen atom transfer process is proposed for the OH product pathway for methyl nitrite, which has been compared with the potential energy surfaces obtained from density functional theory (DFT) calculations. A photodissociation mechanism of n-butyl nitrite is also proposed for the OH product pathway, which differs from that of methyl nitrite due to the effects of the different alkoxy substituents.
语种英语
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WOS记录号WOS:000264805500001
引用统计
被引频次:11[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/101613
专题中国科学院大连化学物理研究所
通讯作者Han KL(韩克利)
作者单位Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
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Yue, Xian-Fang,Sun, Ju-Long,Yin, Hong-Ming,et al. Photodissociation Dynamics of Alkyl Nitrites at 266 and 355 nm: The OH Product Channel[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2009,113(14):3303-3310.
APA Yue, Xian-Fang,Sun, Ju-Long,Yin, Hong-Ming,Wei, Qiang,Han, Ke-Li,&韩克利.(2009).Photodissociation Dynamics of Alkyl Nitrites at 266 and 355 nm: The OH Product Channel.JOURNAL OF PHYSICAL CHEMISTRY A,113(14),3303-3310.
MLA Yue, Xian-Fang,et al."Photodissociation Dynamics of Alkyl Nitrites at 266 and 355 nm: The OH Product Channel".JOURNAL OF PHYSICAL CHEMISTRY A 113.14(2009):3303-3310.
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