The gas phase reaction of C2H+2 with H2 below 3 K: The reopening of the bimolecular C2H+3 channel at low energy
The gas phase reaction of C2H+2 with H2 below 3 K: The reopening of the bimolecular C2H+3 channel at low energy
复制标题
C2H 2 与H2在3 K以下的气相反应：低能下双分子C2H 3 通道的重新打开
DOI：
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发表时间：
1992
期刊：
影响因子：
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通讯作者：
M. Smith
中科院分区：
文献类型：
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作者：
M. Hawley;M. Smith
在自由射流反应器中观察到，在3K以下，C2H+2与H2的双分子反应发生了惊人的机理转变，转变为与能量成反比的反应。在此能量范围内，观测到的C2H+3生成速率系数为k=5.6×10−11T−2 cm~3/S。与以前的看法相反，该反应是放热的，并描述了关于动力学同位素效应、竞争性三体缔合过程和化学的内部C2H+2振动态依赖的结果。提出了一种机制，它涉及通过小势垒低温切换到隧道过程，并与极低能量碰撞的长寿命复杂性质密切耦合。
The bimolecular reaction of C2H+2 with H2 is found to undergo a surprising change of mechanism to one of inverse energy dependence below temperatures of 3 K as observed in a free jet flow reactor. The observed rate coefficient for C2H+3 production is found to be k=5.6×10−11 T−2 cm3/s in this energy regime. Contrary to previous belief, the reaction is exothermic and results are described regarding kinetic isotope effects, the competitive three body association process and internal C2H+2 vibrational state dependency of the chemistry. A mechanism is suggested which involves a low temperature switching to a tunneling process through a small barrier and is intimately coupled to the long lived complex properties of very low energy collisions.