Gibbard, Jemma A. and Verlet, Jan R. R. (2022) 'Kasha’s Rule and Koopmans’ Correlations for Electron Tunnelling through Repulsive Coulomb Barriers in a Polyanion.', The Journal of Physical Chemistry Letters, 13 (33). pp. 7797-7801.
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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|Publisher Web site:||https://doi.org/10.1021/acs.jpclett.2c02145|
|Publisher statement:||This is an Open Access article distributed under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse, distribution, and reproduction in any medium, provided the original work is properly cited.|
|Date accepted:||11 August 2022|
|Date deposited:||06 September 2022|
|Date of first online publication:||16 August 2022|
|Date first made open access:||06 September 2022|
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