Kasha's Rule and Koopmans' Correlations for Electron Tunnelling through Repulsive Coulomb Barriers in a Polyanion.

Kasha's Rule and Koopmans' Correlations for Electron Tunnelling through Repulsive Coulomb Barriers in a Polyanion.
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DOI:
10.1021/acs.jpclett.2c02145
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发表时间:
2022-08-25
影响因子:
5.7
通讯作者:
Verlet, Jan R. R.
Verlet, Jan R. R.
中科院分区:
化学2区
文献类型:
--
作者:
Gibbard, Jemma A.;Verlet, Jan R. R.

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聚阴离子的长程电子结构由排斥库仑势垒(RCB)定义。激发态可以通过RCB的共振电子隧穿而衰减,但除了第一激发态之外,还没有观察到电子激发态的这种衰减,这表明共振电子隧穿的Kasha型规则。使用行动光谱,光电子成像,和计算化学,我们表明,荧光素二价阴离子,F1 2-,部分衰变通过电子隧道从S2激发态,从而证明反Kasha行为,共振电子隧道坚持Koopmans的相关性,从而解开不同的渠道。
The long-range electronic structure of polyanions is defined by the repulsive Coulomb barrier (RCB). Excited states can decay by resonant electron tunnelling through RCBs, but such decay has not been observed for electronically excited states other than the first excited state, suggesting a Kasha-type rule for resonant electron tunnelling. Using action spectroscopy, photoelectron imaging, and computational chemistry, we show that the fluorescein dianion, Fl2–, partially decays through electron tunnelling from the S2 excited state, thus demonstrating anti-Kasha behavior, and that resonant electron tunnelling adheres to Koopmans’ correlations, thus disentangling different channels.
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