We treat the competition between autodetachment of electrons and unimolecular dissociation of excited molecular anions as a rigid-/loose-activated complex multichannel reaction system. To start, the temperature and pressure dependences under thermal excitation conditions are represented in terms of falloff curves of separated single-channel processes within the framework of unimolecular reaction kinetics. Channel couplings, caused by collisional energy transfer and "rotational channel switching" due to angular momentum effects, are introduced afterward. The importance of angular momentum considerations is stressed in addition to the usual energy treatment. Non-thermal excitation conditions, such as typical for chemical activation and complex-forming bimolecular reactions, are considered as well. The dynamics of excited SF6- anions serves as the principal example. Other anions such as CF3- and POCl3- are also discussed.

中文翻译：

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电子自解离与分子阴离子解离之间的竞争。

我们将电子的自动分离与激发的分子阴离子的单分子解离之间的竞争视为刚性/松散活化的复杂多通道反应系统。首先，在单分子反应动力学的框架内，以分离的单通道过程的衰减曲线表示热激发条件下的温度和压力依赖性。随后介绍由碰撞能量转移和由于角动量效应引起的“旋转通道切换”引起的通道耦合。除了通常的能量处理之外，还强调了角动量考虑的重要性。还考虑了非热激发条件，例如化学活化和形成复合物的双分子反应的典型条件。激发的SF6-阴离子的动力学是主要的例子。还讨论了其他阴离子，例如CF3-和POCl3-。