Excited States in Electron-Transfer Reaction Products: Ultrafast Relaxation Dynamics of an Isolated Acceptor Radical Anion

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...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-08, Vol.115 (30), p.8369-8374
Main Authors: Horke, Daniel A, Roberts, Gareth M, Verlet, Jan R. R
Format: Article
Language:English
Subjects:
A: Dynamics, Clusters, Excited States
Anions
Displays
Dynamics
Excitation
Excitation spectra
Ground state
Radicals
Spectroscopy
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Summary: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.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp2038202