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

Gibbard, Jemma A.; Verlet, Jan R.R.

doi:10.1021/acs.jpclett.2c02145

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

Gibbard, Jemma A.; Verlet, Jan R.R.

Authors

Dr Jemma Gibbard jemma.gibbard@durham.ac.uk
Royal Society University Research Fellow

Professor Jan Verlet j.r.r.verlet@durham.ac.uk
Professor

Abstract

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.

Citation

Gibbard, J. A., & Verlet, J. R. (2022). Kasha’s Rule and Koopmans’ Correlations for Electron Tunnelling through Repulsive Coulomb Barriers in a Polyanion. Journal of Physical Chemistry Letters, 13(33), 7797-7801. https://doi.org/10.1021/acs.jpclett.2c02145

Journal Article Type	Article
Acceptance Date	Aug 11, 2022
Online Publication Date	Aug 16, 2022
Publication Date	2022
Deposit Date	Sep 6, 2022
Publicly Available Date	Sep 6, 2022
Journal	The Journal of Physical Chemistry Letters
Electronic ISSN	1948-7185
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	13
Issue	33
Pages	7797-7801
DOI	https://doi.org/10.1021/acs.jpclett.2c02145

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