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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Dissociation Pathways of the CH2CH2ONO Radical: NO2 + Ethene, NO plus Oxirane, and a Non-Intrinsic Reaction Coordinate HNO plus Vinoxy Pathway
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Dissociation Pathways of the CH2CH2ONO Radical: NO2 + Ethene, NO plus Oxirane, and a Non-Intrinsic Reaction Coordinate HNO plus Vinoxy Pathway

机译：CH2CH2ONO自由基的离解途径：NO2 +乙烯，NO加环氧乙烷和非本征反应坐标HNO加乙烯基通道

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摘要

We first characterize the dissociation pathways of BrCH2CH2ONO, a substituted alkyl nitrite, upon photoexcitation at 193 nm under collision-free conditions, in a crossed laser-molecular beam scattering apparatus using vacuum ultraviolet photoionization detection. Three primary photodissociation pathways occur: photo elimination of HNO, leading to the products HNO + BrCH2CHO; C-Br bond photofission, leading to Br + CH2CH2ONO; and O-NO bond photofission, leading to NO + BrCH2CH2O. The data show that alkyl nitrites can eliminate HNO via a unimolecular mechanism in addition to the commonly accepted bulk disproportionation mechanism. Some of the products from the primary photodissociation pathways are highly vibrationally excited, so we then probe the product branching from the unimolecular dissociation of these unstable intermediates. Notably, the vibrationally excited CH2CH2ONO radicals undergo two channels predicted by statistical transition state theory, and an additional non-intrinsic reaction coordinate channel, HNO elimination. CH2CH2ONO is formed with high rotational energy; by employing rotational models based on conservation of angular momentum, we predict, and verify experimentally, the kinetic energies of stable CH2CH2ONO radicals and the angular distribution of dissociation products. The major dissociation pathway of CH2CH2ONO is NO2 + ethene, and some of the NO2 is formed with sufficient internal energy to undergo further photodissociation. Nascent BrCH2CHO and CH2Br are also photodissociated upon absorption of a second 193 nm photon; we derive the kinetic energy release of these dissociations based on our data, noting similarities to the analogous photodissociation of ClCH2CHO and CH2Cl.
机译：我们首先表征了在无碰撞条件下，在交叉激光-分子束散射仪中使用真空紫外光电离检测在193 nm进行光激发时，BrCH2CH2ONO（一种取代的亚硝酸烷基酯）BrCH2CH2ONO的离解途径。发生三种主要的光解离途径：HNO的光消除，导致生成HNO + BrCH2CHO产物; C-Br键光裂变，导致Br + CH2CH2ONO;和O-NO键的光裂变，导致NO + BrCH2CH2O。数据表明，亚硝酸烷基酯除了可以普遍接受的整体歧化机理外，还可以通过单分子机理消除HNO。来自主要光解离途径的一些产物被高度振动激发，因此我们随后研究了这些不稳定中间体的单分子解离所产生的产物。值得注意的是，振动激发的CH2CH2ONO自由基经历两个通过统计跃迁状态理论预测的通道，另外一个非本征反应坐标通道，即HNO消除。 CH2CH2ONO具有高旋转能;通过采用基于角动量守恒的旋转模型，我们预测并实验验证了稳定的CH2CH2ONO自由基的动能和解离产物的角度分布。 CH2CH2ONO的主要离解途径是NO2 +乙烯，并且一些NO2的形成具有足够的内能以进行进一步的光解离。吸收第二个193 nm光子后，新生的BrCH2CHO和CH2Br也被光解离;我们基于我们的数据推导了这些离解的动能释放，并指出了其与ClCH2CHO和CH2Cl的类似光解离的相似性。

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