论文标题
CH3NC自由基阳离子的分子内重排
Femtosecond intramolecular rearrangement of the CH3NCS radical cation
论文作者
论文摘要
强场电离，涉及隧道电离和电子脱落，使飞秒时间分辨的动力学测量涉及自由基阳离子的化学反应。在这里，我们比较了Isomers CH3SCN和CH3NC的强场电离后的CH3S+的形成。前者涉及中性CN的释放，而后者涉及分子内重排。我们发现分子内的重排发生在单比秒时间尺度上，并表现出振动连贯性。密度功能理论和对中性和单动物种的耦合群集计算有助于我们确定负责CH3NC中分子内重排的驱动力。我们的发现说明了电子电离后自由基阳离子化学伴随的复杂性，并展示了一种有用的工具，可以理解电离后阳离子动力学。
Strong-field ionization, involving tunnel ionization and electron rescattering, enables femtosecond time-resolved dynamics measurements of chemical reactions involving radical cations. Here, we compare the formation of CH3S+ following the strong-field ionization of the isomers CH3SCN and CH3NCS. The former involves the release of neutral CN, while the latter involves an intramolecular rearrangement. We find the intramolecular rearrangement takes place on the single picosecond timescale and exhibits vibrational coherence. Density functional theory and coupled-cluster calculations on the neutral and singly ionized species help us determine the driving force responsible for intramolecular rearrangement in CH3NCS. Our findings illustrate the complexity that accompanies radical cation chemistry following electron ionization and demonstrate a useful tool for understanding the cation dynamics after ionization.
