Temporary Anion Resonances of Pyrene: A 2D Photoelectron Imaging and Computational Study
Temporary Anion Resonances of Pyrene: A 2D Photoelectron Imaging and Computational Study
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DOI：
10.1021/acs.jpca.1c05586
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发表时间：
2021-08-09
影响因子：
2.9
通讯作者：
Jordan, Kenneth D.
中科院分区：
文献类型：
--
作者：
Lietard, Aude;Verlet, Jan R. R.;Jordan, Kenneth D.
利用实验和计算方法对芘的低能电子散射共振进行了表征。实验上，利用芘阴离子的二维光电子成像来探测连续体前4ev的共振动力学。在计算上，使用运动方程耦合簇计算确定阴离子态的能量和特征，同时特别注意避免崩溃到离散的连续体水平，并应用配对定理。我们的结果很好地符合电子散射计算的预测，包括偏移和玻璃基体中的芘阴离子吸收光谱。综上所述，我们给出了芘的前五个电子共振的分配。在最低能量的B-2（1u）共振中，观察到一些居群衰变到阴离子的基电子态，而所有其他共振都是直接自脱离衰变。讨论了在芘中通过低能共振进行基态电子捕获的天文学意义。
The low-energy electron-scattering resonances of pyrene were characterized using experimental and computational methods. Experimentally, a two-dimensional photoelectron imaging of the pyrene anion was used to probe the dynamics of resonances over the first 4 eV of the continuum. Computationally, the energies and character of the anion states were determined using equation-of-motion coupled cluster calculations, while taking specific care to avoid the collapse onto discretized continuum levels, and an application of the pairing theorem. Our results are in good agreement with the predictions of electron-scattering calculations that include an offset and with the pyrene anion absorption spectrum in a glass matrix. Taken together, we offer an assignment of the first five electronic resonances of pyrene. Some of the population in the lowest-energy B-2(1u) resonance was observed to decay to the ground electronic state of the anion, while all other resonances decay by a direct autodetachment. The astronomical relevance of a ground-state electron capture proceeding via a low-energy resonance in pyrene is discussed.