Publication details for Prof. Jan R.R. VerletHorke, D.A., Roberts, G.M. & Verlet, J.R.R. (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.
- Publication type: Journal Article
- ISSN/ISBN: 1089-5639 (print), 1520-5215 (electronic)
- DOI: 10.1021/jp2038202
- Further publication details on publisher web site
- Durham Research Online (DRO) - may include full text
Author(s) from Durham
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.