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Photodissociation Dynamics of Nitromethane and Nitroethane at 266 nm
Xian-fang Yue, Ju-long Sun, Qiang Wei, Hong-ming Yin, Ke-li Han*
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Abstract:
Measurements of the nascent OH product from photodissociation of gaseous nitromethane and nitroethane at 266 nm were performed using the single-photon laser induced °uorescence technique. The OH fragment is found to be vibrationally cold for both systems. The rotational state distribution of nitromethane are Boltzmann, with rotational temperature of Trot=2045§150 and 1923§150 K for both 2|3=2 and 2|1=2 states, respectively. For nitroethane, the rotational state distribution shows none Boltzmann and cannot be well characterized by a rotational temperature, which indicates the di?erent mechanisms in producing OH radicals from photodissociation of nitromethane and nitroethane. The rotational energy is calculated as 14.36§0.8 and 4.98§0.8 kJ/mol for nitromethane and nitroethane, respectively. A preferential population of the low spin-orbit component (2|3=2) is observed for both nitromethane and nitroethane. The dominant population of |+ state in two ¤-doublet states is also observed for both nitromethane and nitroethane, which indicates that the unpaired ? lobe of the OH fragment is parallel to the plane of rotation.
Key words:  Photodissociation dynamics, Single-photon laser induced °uorescence, Nitromethane, Nitroethane
FundProject:国家基础研究重大项目基金
硝基甲烷与硝基乙烷266 nm光解动力学
岳现房, 孙巨龙, 魏强, 尹鸿鸣, 韩克利*
中国科学院大连化学物理研究所分子反应动力学国家重点实验室,大连116023
摘要:
利用单光子激光诱导荧光技术,在硝基甲烷与硝基乙烷气相条件下266 nm光解过程中,对初生态的解离产物OH进行了测量.结果表明,两个解离过程中产生的初生态OH都没有振动激发.硝基甲烷光解过程中产生的OH的转动分布可以用玻尔兹曼温度简单的表示,相对于自旋轨道分裂的2|3=2与2|1=2两个态,其转动温度分别为2045§150与1923§150 K.硝基乙烷光解过程中产生的OH不是简单的玻尔兹曼分布,因此不能用玻尔兹曼温度来描述,这一结果 意味着硝基甲烷与硝基乙烷在生成OH的过程中经历了不同的解离过程.硝基甲烷
关键词:  光解动力学,单光子激光诱导荧光,硝基甲烷,硝基乙烷
DOI:10.1088/1674-0068/20/04/401-406
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