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.