Pyla Maneesh, Matsika Spiridoula
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.
J Chem Phys. 2024 Oct 21;161(15). doi: 10.1063/5.0232581.
Electron attachment to pyridine results in electronic resonances, metastable states that can decay through electronic or nuclear degrees of freedom. This study uses orbital stabilization techniques combined with bound electronic structure methods, based on equation of motion coupled cluster or multi-reference methods, to calculate positions and widths of electronic resonances in pyridine that exist below 10 eV. We report four 2B1 and four 2A2 resonances, including one 2B1 not previously reported experimentally and two 2A2 resonances not reported at all in the literature. The two lower energy resonances are one-particle shape resonances, while the remaining are mixed or primarily core-excited resonances. Multi-reference perturbation theory provides the best description of these resonances, especially when their character is mixed. We describe the character of these resonances qualitatively and calculate Dyson orbitals, which provide information about their decay channels.
电子附着到吡啶上会产生电子共振，即可以通过电子或核自由度衰变的亚稳态。本研究使用轨道稳定技术并结合基于运动方程耦合簇或多参考方法的束缚电子结构方法，来计算吡啶中能量低于10电子伏特的电子共振的位置和宽度。我们报告了四个2B1和四个2A2共振，其中包括一个之前未通过实验报道的2B1和两个文献中完全未报道的2A2共振。两个能量较低的共振是单粒子形状共振，而其余的是混合或主要为芯激发共振。多参考微扰理论对这些共振提供了最佳描述，尤其是当它们的特征是混合的时候。我们定性地描述了这些共振的特征，并计算了戴森轨道，其提供了有关它们衰变通道的信息。
