10.1021/jp2038202.s001
Daniel A. Horke
Daniel A.
Horke
Gareth M. Roberts
Gareth M.
Roberts
Jan R. R. Verlet
Jan
R. R. Verlet
Excited States in Electron-Transfer Reaction Products: Ultrafast Relaxation Dynamics of an Isolated Acceptor Radical Anion
American Chemical Society
2011
200 fs
ultrafast relaxation dynamics
anion ground state
Isolated Acceptor Radical AnionThe spectroscopy
energy state
displays rates
60 fs time scale
Ultrafast Relaxation Dynamics
photoelectron spectra
gas phase
Excited States
2011-08-04 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Excited_States_in_Electron_Transfer_Reaction_Products_Ultrafast_Relaxation_Dynamics_of_an_Isolated_Acceptor_Radical_Anion/2626464
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.