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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photodissociation of Unsaturated Alcohols.Energy Distribution in the Nascent OH Radicals
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Photodissociation of Unsaturated Alcohols.Energy Distribution in the Nascent OH Radicals

机译：不饱和醇的光解离。新生OH自由基中的能量分布

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摘要

The photodissociation of allyl and propargyl alcohols at 193 nm,which involves pi-pi electronic transition and leads to the formation of OH,has been studied by using a laser photolysis-laser-induced fluorescence technique.The nascent OH radicals formed from both these molecules are found to be rotationally and vibrationally excited.The vibrational distributions are found to be similar,described by vibrational temperatures of 2070+-380 and 2130+-440 K for allyl and propargyl alcohols,respectively.The rotational temperatures of both upsilon"=0 and 1 levels of OH radicals from allyl alcohol are found to be almost the same,viz.,1960+-150 and 1900+-250 K,respectively,and close to the vibrational temperature.On the other hand,the rotational temperatures of OH radicals,1760+-130 K at the upsilon"=0 level and 690+-120 K at the upsilon"=1 level,are very different from each other,in the case of propargyl alcohol.In both molecules,a significant part of the available energy is partitioned into the relative translational energy of the fragments,118.4+-22.2 and 148.0+-23.0 kJ mol~(-1) in allyl and propargyl alcohols,respectively.The results indicate a quantitative difference in the energy partitioning within the fragments of the two molecules,and only a hybrid model involving an exit barrier can explain the observations.
机译：利用激光光解-激光诱导荧光技术研究了烯丙基和炔丙醇在193 nm处的光解离，涉及pi-pi电子跃迁并导致OH的形成。这两个分子形成的新生OH自由基发现振动分布是相似的，发现对于烯丙醇和炔丙基醇的振动温度是相似的，分别由2070 + -380和2130 + -440 K的振动温度来描述。两个upsilon的旋转温度“ = 0与烯丙醇的1个OH自由基的水平几乎相同，即1960 + -150和1900 + -250 K，并且接近振动温度。另一方面，OH的旋转温度在炔丙基醇的情况下，自由基“ = 0”处的基团为1760 + -130 K，而“硅烷” = 1处的基团为690 + -120 K彼此非常不同。在两个分子中，可用能量被划分为分别在烯丙醇和炔丙醇中片段的相对翻译能118.4 + -22.2和148.0 + -23.0 kJ mol〜（-1）。结果表明两个分子片段中的能量分配存在定量差异，并且只有包含出口障碍的混合模型才能解释这些观察结果。

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