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首页> 外文期刊>The Journal of Chemical Physics >Ring-opening attachment as an explanation for the long lifetime of the octafluorooxolane anion
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Ring-opening attachment as an explanation for the long lifetime of the octafluorooxolane anion

机译：开环附件作为八氟毒性阴离子的长寿命的解释

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Octafluorooxalane, C4F8O, has recently attracted attention as a possible replacement of SF6 in high voltage insulation, and its reactivity with respect to free-electron attachment was investigated by mass spectrometry. The most intense signal peaks at 0.9 eV and corresponds to the parent anion, C4F8O-; fragments stemming from complex breakup reactions are detected starting above similar to 1.6 eV. Since parent anions in free-electron attachment are normally associated with threshold attachment or an embedding environment allowing excess energy deposition, this observation is highly unusual. Based on density functional calculations, it was nevertheless interpreted as attachment followed by intermolecularvibrational-relaxation. Here, electron-attachment to octafluorooxalane is studied computationally. First, the electron affinity (EA) is characterized using density functionals and ab initio methods. Moreover, the negative vertical EA is estimated by extrapolating electron binding energies computed in the vicinity of C4F8O- to the geometry of neutral octafluorooxalane. Then, alternative explanations for the 0.9 eV peak are considered. Specifically, a ring-opening reaction that yields a distonic isomer of C4F8O- is identified. Our analysis reveals that the chain isomer possesses many conformers, all of which are considerably more stable than the ring isomer, and that the time scale for the unimolecular ring opening reaction is significantly faster than 1 mu s. Thus, at the experimental energy, the ring isomer of C4F8O- is predicted to convert practically completely into the chain isomer, and we argue that the long lifetime and the peak position are effectively determined by the properties of the ring-opening transition state. Published by AIP Publishing.
机译：OctafluoroOxalane，C4F8O最近引起了在高压绝缘中的可能更换SF6的关注，并通过质谱法研究了其相对于自由电子附着的反应性。在0.9eV的最强烈信号峰值，对应于父母阴离子，C4F8O-;检测到从复杂分发反应的碎片开始，起始于上面类似于1.6eV。由于自由电子附件中的父阴离子通常与阈值附件或嵌入环境相关联，因此这种观察非常不寻常。基于密度函数计算，仍然被解释为附件，然后是分体体振荡弛豫。这里，计算到八氟氧氧氧烷的电子连接。首先，使用密度函数和AB Initio方法表征电子亲和力（EA）。此外，通过将C4F80附近的电子结合能推断为中性八键氧氧氧氧氧氧氧鎓的几何形状来估计负垂直EA。然后，考虑0.9eV峰的替代解释。具体地，鉴定了产生C4F8O-的辐射异构体的开环反应。我们的分析表明，链异构体具有许多相符，所有这些都比环异构体相当稳定，并且单分子开环反应的时间标度明显快于1μs。因此，在实验能量下，预计C4F8O-的环形异构体实际上是完全转换成链式异构体，并且我们认为长寿和峰值位置通过开环过渡状态的性质有效地确定。通过AIP发布发布。

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