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Determining the Partial Photoionization Cross-Sections of Ethyl Radicals

机译:确定乙基自由基的部分光电离截面

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Using a crossed laser-molecular beam scattering apparatus,these experiments photodissociate ethyl chloride at 193 nm and detect the Cl and ethyl products,resolved by their center-of-mass recoil velocities,with vacuum ultraviolet photoionization.The data determine the relative partial cross-sections for the photoionization of ethyl radicals to form C2H_5~+,C2H_4~+,and C2H_3~+at 12.1 and 13.8 eV.The data also determine the internal energy distribution of the ethyl radical prior to photoionization,so we can assess the internal energy dependence of the photoionization cross-sections.The results show that the C2H_4~++H and C2H_3~++H2 dissociative photoionization cross-sections strongly depend on the photoionization energy.Calibrating the ethyl radical partial photoionization cross-sections relative to the bandwidth-averaged photoionization cross-section of Cl atoms near 13.8 eV allows us to use these data in conjunction with literature estimates of the Cl atom photoionization cross-sections to put the present bandwidth-averaged cross-sections on an absolute scale.The resulting bandwidth-averaged cross-section for the photoionization of ethyl radicals to C2H_5~+near 13.8 eV is 8±2 Mb.Comparison of our 12.1 eV data with high-resolution ethyl radical photoionization spectra allows us to roughly put the high-resolution spectrum on the same absolute scale.Thus,one obtains the photoionization cross-section of ethyl radicals to C2H_5~+from threshold to 12.1 eV.The data show that the onset of the C2H_4~++H dissociative photoionization channel is above 12.1 eV;this result offers a simple way to determine whether the signal observed in photoionization experiments on complex mixtures is due to ethyl radicals.We discuss an application of the results for resolving the product branching in the O+allyl bimolecular reaction.
机译:这些实验使用交叉激光分子束散射仪,在193 nm处将氯乙烷光解离并检测Cl和乙基产物,并通过质心反冲速度将其分离,并进行真空紫外光电离。数据确定相对部分交叉分别在12.1和13.8 eV处对乙基进行离子化以形成C2H_5〜+,C2H_4〜+和C2H_3〜+的截面。这些数据还确定了在光电离之前乙基的内部能分布,因此我们可以评估内部能结果表明,C2H_4〜++ H和C2H_3〜++ H2离解型光电离截面强烈依赖于光电离能。校准乙基部分光电离截面相对于带宽- Cl原子在13.8 eV附近的平均光电离截面使我们可以将这些数据与Cl原子光电离截面的文献估计结合起来使用将当前的带宽平均横截面以绝对比例表示。将乙基光电离为C2H_5〜+ 13.8 eV所得到的带宽平均横截面为8±2 Mb。我们的12.1 eV数据与高分辨率的乙基光电离光谱使我们能够大致将高分辨率光谱置于相同的绝对尺度上。因此,人们获得了从阈值到12.1 eV的C2H_5〜+自由基的光电离截面。 C2H_4〜++ H离解光电离通道的电离高于12.1 eV;该结果提供了一种简单的方法来确定复杂混合物在光电离实验中观察到的信号是否是由于乙基引起的。我们讨论了该结果在拆分产物中的应用在O +烯丙基双分子反应中分支。

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