%0 Journal Article %A Horke, Daniel A. %A Roberts, Gareth M. %A R. R. Verlet, Jan %D 2011 %T Excited States in Electron-Transfer Reaction Products: Ultrafast Relaxation Dynamics of an Isolated Acceptor Radical Anion %U https://acs.figshare.com/articles/journal_contribution/Excited_States_in_Electron_Transfer_Reaction_Products_Ultrafast_Relaxation_Dynamics_of_an_Isolated_Acceptor_Radical_Anion/2626464 %R 10.1021/jp2038202.s001 %2 https://acs.figshare.com/ndownloader/files/4277146 %K 200 fs %K ultrafast relaxation dynamics %K anion ground state %K Isolated Acceptor Radical AnionThe spectroscopy %K energy state %K displays rates %K 60 fs time scale %K Ultrafast Relaxation Dynamics %K photoelectron spectra %K gas phase %K Excited States %X 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. %I ACS Publications