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.

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
• Public URL: https://durham-repository.worktribe.com/output/1488560