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

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, Fl^2-, 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.