The mechanism of the unimolecular dissociation of trichloroethylene CHCl=CCl2 in the ground electronic state
The mechanism of the unimolecular dissociation of trichloroethylene CHCl=CCl2 in the ground electronic state
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DOI：
10.1063/1.468989
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发表时间：
1995-05
影响因子：
4.4
通讯作者：
K. Yokoyama;G. Fujisawa;A. Yokoyama
中科院分区：
文献类型：
--
作者：
K. Yokoyama;G. Fujisawa;A. Yokoyama
利用红外多光子解离结合光碎片平动光谱法测量产物平动能，研究了三氯乙烯在电子基态下的单分子解离。根据观察到的产物飞行时间（TOF）光谱，发现主要的反应通道是HCl的消除。该通道的质心平动能量分布为两通道、三中心和四中心HCl消去之间的竞争提供了直接证据。从观察到的Cl+和C2HCl+TOF光谱中发现Cl消除是一个次要但重要的通道。三中心和四中心HCl消去和Cl消去的分支比分别为0.28、0.55和0.17。三中心通道表现出“统计”的平动能量分布，这是逆反应中没有势能势垒的典型反应，也就是说，没有出口势垒反应。在…
The unimolecular dissociation of trichloroethylene in its electronic ground state has been investigated using an infrared multiphoton dissociation combined with photofragmentation translational spectroscopy to measure product translational energies. The main reaction channel was found to be HCl elimination on the basis of observed product time‐of‐flight (TOF) spectra. A center‐of‐mass translational energy distribution for this channel provides direct evidence for competition between two channels, three‐ and four‐centered HCl eliminations. Cl elimination was found to be a minor but significant channel from observed Cl+ and C2HCl+TOF spectra. The branching ratios were determined as 0.28, 0.55, and 0.17 for the three‐ and four‐centered HCl eliminations and the Cl elimination, respectively. The three‐centered channel exhibits a ‘‘statistical’’ translational energy distribution which is typical for a reaction with no potential energy barrier in the reverse reaction, that is to say, no exit barrier reaction. In...