Photoelectron angular distributions in photodetachment from polarised d -like states: the case of HO 2 −
Photoelectron angular distributions in photodetachment from polarised d -like states: the case of HO 2 −
复制标题
偏振 d 态光脱离中的光电子角分布：HO 2 的情况 —
DOI：
10.1080/00268976.2020.1831636
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发表时间：
2021
影响因子：
1.7
通讯作者：
Sanov, Andrei
中科院分区：
文献类型：
--
作者：
Blackstone, Christopher C.;Wallace, Adam A.;Sanov, Andrei
我们对HO 2-光分离中的角分布进行了光电子成像研究。所研究的跃迁对应于HO 2 −的电子从a“HOMO和”HOMO−1脱离，产生处于基态和第一激发电子态的中性过氧氢自由基。用混合态光剥离一般模型的p-d变量对实验结果进行了分析。在这个模型中，母阴离子分子轨道或相应的Dyson轨道被描述为放置在分子框架中的一个选定的中心的atomicpandd函数的叠加。由于光电子角分布对母轨道的长程标度很敏感，因此对实验结果进行建模可以深入了解阴离子波函数的渐近行为。在该模型中，扩散轨道的长程行为使用定义基函数的有效电荷进行参数化。这些参数不对应于阴离子中的物理电荷，但描述了模型函数的thepandd分量的长程标度，因此，母阴离子轨道。HO 2 −的实验和模型结果与NO−和O2−进行了比较，揭示了分子对称性和化学键结构对光电子角分布的影响。
We present a photoelectron imaging study of the angular distributions in HO2−photodetachment. The transitions studied correspond to electron detachment from thea″HOMO anda′ HOMO−1 of HO2−, yielding the neutral hydroperoxy radical in the ground and first excited electronic states. The experimental results are analysed using thep-dvariant of the general model for photodetachment from mixed-character states. In this model, the parent anion molecular orbitals or the corresponding Dyson orbitals are described as superpositions of atomicpanddfunctions placed at a chosen centre in the molecular frame. As photoelectron angular distributions are sensitive to the long-range scaling of the parent orbitals, modelling the experimental results yields insight into the asymptotic behaviour of anionic wavefunctions. In the model, the long-range behaviour of diffuse orbitals is parameterised using the effective charges defining the basis functions. These parameters do not correspond to physical charges in the anion, but describe the long-range scaling of thepanddcomponents of the model function and, therefore, the parent anion orbital. The experimental and model results for HO2−are compared to NO−and O2−, shedding light on the effects of molecular symmetry and chemical bonding structures on the photoelectron angular distributions.