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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Dissociative Photoionization of the Elusive Vinoxy Radical
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Dissociative Photoionization of the Elusive Vinoxy Radical

机译：难以消除的难以捉摸的芳氧基自由基

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These experiments report the dissociative photoionization of vinoxy radicals to m/z = 15 and 29. In a crossed laser molecular beam scattering apparatus, we induce C-Cl bond fission in 2-chloroacetaldehyde by photoexcitation at 157 nm. Our velocity measurements, combined with conservation of angular momentum, show that 21% of the C-Cl photofission events form vinoxy radicals that are stable to subsequent dissociation to CH3 + CO or H + ketene. Photoionization of these stable vinoxy radicals, identified by their velocities, which are momentum-matched with the higher-kinetic energy Cl atom photofragments, shows that the vinoxy radicals dissociatively photoionize to give signal at m/z = 15 and 29. We calibrated the partial photoionization cross section of vinoxy to CH3+ relative to the bandwidth-averaged photoionization cross section of the Cl atom at 13.68 eV to put the partial, photoionization cross sections on an absolute scale. The resulting bandwidth-averaged partial cross sections are 0.63 and 1.3 Mb at 10.5 and 11.44 eV, respectively. These values are consistent with the upper limit to the cross section estimated from a study by Savee et al. on the O(P-3) + propene bimolecular reaction. We note that the uncertainty in these values is primarily dependent on the signal attributed to C-Cl primary photofission in the m/z = 35 (Cl+) time-of-flight data. While the value is a rough estimate, the bandwidth-averaged partial photoionization cross section of vinoxy to HCO+ calculated from the signal at m/z = 29 at 11.53 eV is approximately half that of vinoxy to CH3+. We also present critical points on the potential energy surface of the vinoxy cation calculated at the G4//B3LYP/6-311++G(3df,2p) level of theory to support the observation of dissociative ionization of vinoxy to both CH3+ and HCO+.
机译：这些实验报告了芳氧基自由基的解离光照化至M / Z = 15和29.在交叉的激光分子束散射装置中，我们通过157nm的光透镜诱导2-氯丙醛中的C-Cl键裂变。我们的速度测量与角动力的保护相结合，表明，21％的C-Cl光缺失事件形成芳氧基自由基，其稳定，以随后对CH3 + CO或H +氯酸酯进行稳定。通过它们的速度鉴定的这些稳定的芳氧基自由基的光离子，其与高动能Cl原子的速度相匹配，表明芳氧基自由基分解光相过度，以在m / z = 15和29处给出信号。我们校准部分通过13.68eV的CL原子的带宽平均光离子横截面的光氧基与CH3 +的光离子横截面以绝对尺度放置部分，光离子横截面。得到的带宽平均分别部分横截面分别为10.5和11.44eV分别为0.63和1.3MB。这些值与Savee等人的研究估计的横截面的上限一致。在O（p-3）+丙烯双分子反应上。我们注意到这些值的不确定性主要取决于M / Z = 35（CL +）飞行时间数据中的C-CL初级光缺陷的信号。虽然该值是粗略估计的虽然，从11.53eV在M / Z = 29的信号中计算的芳氧基与HCO +的带宽平均部分光离子横截面约为磷氧基对CH3 +的一半。我们还存在于在G4 // B3LYP / 6-311 ++ G（3DF，2P）理论水平的载体阳离子的潜在能量表面上的关键点，以支持对CH3 +和HCO +两者的解离电离的观察。

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