J.N. Bull
Internal conversion outcompetes autodetachment from resonances in the deprotonated tetracene anion continuum
Bull, J.N.; West, C.W.; Verlet, J.R.R.
Abstract
Photoelectron velocity-map imaging and electronic structure calculations have been used to study the temporary anion (resonance) dynamics of the closed-shell site-specific deprotonated tetracene anion (C18H11−) in the hv = 3.26 eV (380 nm) to 4.13 eV (300 nm) range. In accord with a recent frequency-, angle-, and time-resolved photoelectron imaging study on a related but open-shell polyaromatic radical anion (Chem. Sci., 2015, 6, 1578–1589), population of π*-resonances situated in the detachment continuum efficiently recover the ground electronic state of the anion through ultrafast non-adiabatic dynamics, followed by characteristic statistical electron loss (thermionic emission). The combined electron yield of direct photodetachment and autodetachment from the optically-accessed resonances in C18H11− is several orders of magnitude smaller than thermionic emission from the ground electronic electronic state in the photon energy range studied. This result implies a resilience to prompt photoejection from UV radiation, and the ability of neutral PAH-like species to capture a free electron and form a long-lived molecular anion that ultimately decays by thermionic emission on a millisecond timescale. The attachment mechanism applies to polyaromatic species that cannot support dipole-bound states, and may provide an additional route to forming anions in astrochemical environments.
Citation
Bull, J., West, C., & Verlet, J. (2015). Internal conversion outcompetes autodetachment from resonances in the deprotonated tetracene anion continuum. Physical Chemistry Chemical Physics, 17(48), 32464-32471. https://doi.org/10.1039/c5cp05388a
Journal Article Type | Article |
---|---|
Acceptance Date | Nov 13, 2015 |
Publication Date | Dec 28, 2015 |
Deposit Date | Dec 18, 2015 |
Publicly Available Date | Mar 29, 2024 |
Journal | Physical Chemistry Chemical Physics |
Print ISSN | 1463-9076 |
Electronic ISSN | 1463-9084 |
Publisher | Royal Society of Chemistry |
Peer Reviewed | Peer Reviewed |
Volume | 17 |
Issue | 48 |
Pages | 32464-32471 |
DOI | https://doi.org/10.1039/c5cp05388a |
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