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Electron ionization of methane: The dissociation of the methane monocation and dication

机译:甲烷电子电离:甲烷单阳离子和离子的离解

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Time-of-flight mass spectrometry and two-dimensional coincidence techniques have been used to determine, for the first time, the relative precursor-specific partial ionization cross sections following electron-methane collisions. Precursor-specific partial ionization cross sections quantify the contribution of single, double, and higher levels of ionization to the partial ionization cross section for forming a specific ion (e.g. CH~+) following electron ionization of methane. Cross sections are presented for the formation of H~+, H_2~+, C~+, CH ~+, CH_2~+, and CH_3~+, relative to CH_4~+, at ionizing electron energies from 30 to 200 eV. We can also reduce our dataset to derive the relative partial ionization cross sections for the electron ionization of methane, for comparison with earlier measurements. These relative partial ionization cross sections are in good agreement with recent determinations. However, we find that there is significant disagreement between our partial ionization cross sections and those derived from earlier studies. Inspection of the values of our precursor-specific partial ionization cross sections shows that this disagreement is due to the inefficient collection of energetic fragment ions in the earlier work. Our coincidence experiments also show that the lower energy electronic states of CH_4~(2+) populated by electron double ionization of CH_4 at 55 eV are the same (ground ~3T _1, first excited ~1E_1) as those populated by 40.8 eV photoionization. The ~3T_1 state dissociating to form CH_3~+ + H~+ and CH_2~+ + H_2~+ and the ~1E_1 to form CH _2~+ + H~+ and CH~+ + H~+. At this electron energy, we also observe population of the first excited triplet state of CH_4~(2+) (~3T_2) which dissociates to both CH_2~+ + H~+ + H and CH ~+ + H~+ + H_2.
机译:飞行时间质谱和二维重合技术已首次用于确定电子-甲烷碰撞后相对前体特定的部分电离截面。前体特定的部分电离截面可量化单电,双级和更高电离水平对部分电离截面的贡献,以便在甲烷电子电离后形成特定离子(例如CH〜+)。给出了在电离电子能量为30至200 eV时,相对于CH_4〜+形成H〜+,H_2〜+,C〜+,CH〜+,CH_2〜+和CH_3〜+的截面。我们还可以简化数据集以得出甲烷电子电离的相对部分电离截面,以便与早期的测量结果进行比较。这些相对的部分电离截面与最近的测定非常吻合。但是,我们发现部分电离截面与早期研究得出的截面存在很大分歧。检查我们的前体特定部分电离截面的值表明,这种分歧是由于早期工作中能量碎片离子的收集效率低下所致。我们的巧合实验还表明,在55 eV处由CH_4的电子双电离形成的CH_4〜(2+)的低能电子态与40.8 eV光电离形成的低能电子态相同(地〜3T _1,首次激发〜1E_1)。 〜3T_1状态解离形成CH_3〜+ + H〜+和CH_2〜+ + H_2〜+,而〜1E_1状态解离形成CH _2〜+ + H〜+和CH〜+ + H〜+。在该电子能量下,我们还观察到CH_4〜(2+)(〜3T_2)的第一激发三重态的种群,该状态三者都离解为CH_2〜+ + H〜+ + H和CH〜+ + H〜+ + H_2。

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