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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >H_2 Production in the 440-nm Photodissociation of Glyoxal
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H_2 Production in the 440-nm Photodissociation of Glyoxal

机译：乙二醛在440-nm光解离中的H_2产生

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摘要

H_2 has been detected following the photolysis of glyoxal at 440 nm using the techniques of vacuum ultraviolet laser-induced fluorescence and (2 + 1) resonance enhanced multiphoton ionization. It is thus confirmed that a fraction of the glyoxal excited at this wavelength dissociates into three photofragments: HCOCOH -> H_2 + 2CO. The most populated vibrational level of those observed was H_2 (v = 1), and in this level rotational states from J = 0-9 were detected. Doppler profiles of these lines provide estimates of the translational energy and show a v||J correlation. Of the available energy to the H_2 + 2CO products, 3.1% appears as rotational energy in H_2 (v = 1), 17.8% appears as the H_2 (v = 1) vibration, and 46.8% appears as H_2 (v = 1) translation. Excitation of the 7_0~2 band produces somewhat more of the H_2 + 2CO channel than does excitation of the 0_0~0, 5_0~1, or 8_0~1 bands. These observations are consistent with a model in which trans -> cis isomerization precedes dissociation. Rotational excitation with v||J is caused by the v_7 torsional motion. The small degree of rotational excitation, the production of H_2 in v = 1 and v = 2, and the translational energy distribution are all consistent with ab initio calculations of the transition state structure.
机译：使用真空紫外激光诱导的荧光和（2 +1）共振增强的多光子电离技术，在440 nm处乙二醛光解后检测到H_2。因此证实了在该波长下激发的乙二醛的一部分解离成三个光碎片段：HCOCOH→H_2 + 2CO。观察到的最高振动水平为H_2（v = 1），在此水平下，检测到J = 0-9的旋转状态。这些线的多普勒轮廓提供了平移能的估计并显示了v || J相关性。在H_2 + 2CO产物的可用能量中，3.1％表示为H_2（v = 1）中的旋转能，17.8％表示为H_2（v = 1）的振动，46.8％表示为H_2（v = 1）的平移。 。与0_0〜0、5_0〜1或8_0〜1频段的激励相比，对7_0〜2频段的激励产生的H_2 + 2CO通道要多一些。这些观察结果与其中反式->顺式异构化先于解离的模型一致。 v_ | J的旋转激励是由v_7扭转运动引起的。小程度的旋转激发，在v = 1和v = 2中H_2的产生以及平移能量分布都与过渡态结构的从头算起是一致的。

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