Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances
Spectroscopy and Theoretical Modeling of Tetracene Anion Resonances
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并四苯阴离子共振的光谱学和理论模型
DOI：
10.1021/acs.jpclett.2c02931
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Garand, Etienne
中科院分区：
文献类型：
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作者：
Sagan, Cole R.;Anstöter, Cate S.;Thodika, Mushir;Wilson, Kenneth D.;Matsika, Spiridoula;Garand, Etienne
的位置和宽度的光学允许的电子状态的并四苯自由基阴离子位于以上的脱离阈值能量（即阴离子共振）的映射出使用低温冷却离子的总光剥离产率光谱。这些状态的存在下，检测通过急剧增加的光剥离产率相比，单调的非共振直接光剥离背景。所得光谱的分辨率受限于可调谐激光器的1.5 cm-1线宽，因此为计算这些共振态的能量和自分离寿命提供了严格的基准。实验结果进行了比较，高层次的电子结构计算和线宽建模使用轨道稳定的方法。这些理论结果被发现是在近定量协议与实验数据，突出了它们的能力，准确地描述相对较大的分子的阴离子共振的能量和寿命。
The positions and widths of the optically allowed electronic states of the tetracene radical anion located above the detachment threshold energy (i.e anion resonances) are mapped out using total photodetachment yield spectroscopy of cryogenically cooled ions. The presence of these states is detected via the sharp increase in the photodetachment yield compared to that of the monotonic nonresonant direct photodetachment background. The resolution of the resulting spectrum is limited by the ∼5 cm–1line width of the tunable laser and thus provides a stringent benchmark for computations of the energies and autodetachment lifetimes of these resonance states. The experimental results are compared to high-level electronic structure computations and line width modeling using the orbital stabilization method. These theoretical results are found to be in near quantitative agreement with the experimental data, highlighting their capability to accurately describe the energies and lifetimes of anion resonances for relatively large molecules.