论文标题
$ ab \ initio $临时阴离子的分子动力学使用复杂的吸收电位
$Ab\ initio$ molecular dynamics of temporary anions using complex absorbing potentials
论文作者
论文摘要
解离电子附件，即低能电子诱导的化学键的裂解，很难用标准的量子化学方法进行建模，因为所涉及的阴离子不受限制，而是经过自动修复。我们在这里提出了一种新的计算开发，用于模拟复杂值势能表面上的临时阴离子的动力学。这些表面的假想部分描述了电子损失，而实际部分的梯度表示核上的力。在我们的方法中，力是根据Hartree-Fock理论进行分析计算的，具有复杂的吸收潜力。 $ aB \ initio $分子动力学模拟，用于二氮，乙烯，氯乙烷和五个单氯化乙烯的临时阴离子，与实验显示了定性的一致性，并提供了对分离性电子附件的机械洞察力。结果还证明了我们的方法如何处理可能会在电子附着以及仅经过自动方案的分子上处理分子。
Dissociative electron attachment, that is, the cleavage of chemical bonds induced by low-energy electrons, is difficult to model with standard quantum-chemical methods because the involved anions are not bound but subject to autodetachment. We present here a new computational development for simulating the dynamics of temporary anions on complex-valued potential energy surfaces. The imaginary part of these surfaces describes electron loss, whereas the gradient of the real part represents the force on the nuclei. In our method, the forces are computed analytically based on Hartree-Fock theory with a complex absorbing potential. $Ab\ initio$ molecular dynamics simulations for the temporary anions of dinitrogen, ethylene, chloroethane, and the five mono- to tetrachlorinated ethylenes show qualitative agreement with experiments and offer mechanistic insights into dissociative electron attachments. The results also demonstrate how our method evenhandedly deals with molecules that may undergo dissociation upon electron attachment and those which only undergo autodetachment.
