Excited States in Electron-Transfer Reaction Products: Ultrafast Relaxation Dynamics of an Isolated Acceptor Radical Anion

Horke, D.A.; Roberts, G.M.; Verlet, J.R.R.

doi:10.1021/jp2038202

Excited States in Electron-Transfer Reaction Products: Ultrafast Relaxation Dynamics of an Isolated Acceptor Radical Anion

Horke, D.A.; Roberts, G.M.; Verlet, J.R.R.

Authors

D.A. Horke

G.M. Roberts

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

Abstract

The spectroscopy and ultrafast relaxation dynamics of excited states of the radical anion of a representative charge-transfer acceptor molecule, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, have been studied in the gas phase using time-resolved photoelectron spectroscopy. The photoelectron spectra reveal that at least two anion excited states are bound. Time-resolved studies show that both excited states are very short-lived and internally convert to the anion ground state, with the lower energy state relaxing within 200 fs and a near-threshold valence-excited state relaxing on a 60 fs time scale. These excited states, and in particular the valence-excited state, present efficient pathways for electron-transfer reactions in the highly exergonic inverted region which commonly displays rates exceeding predictions from electron-transfer theory.

Citation

Horke, D., Roberts, G., & Verlet, J. (2011). Excited States in Electron-Transfer Reaction Products: Ultrafast Relaxation Dynamics of an Isolated Acceptor Radical Anion. The Journal of Physical Chemistry A, 115(30), 8369-8374. https://doi.org/10.1021/jp2038202

Journal Article Type	Article
Publication Date	Aug 4, 2011
Deposit Date	Jan 30, 2012
Publicly Available Date	Feb 5, 2016
Journal	The Journal of Physical Chemistry A
Print ISSN	1089-5639
Electronic ISSN	1520-5215
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	115
Issue	30
Pages	8369-8374
DOI	https://doi.org/10.1021/jp2038202

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jp2038202.