UNIGE document Scientific Article
previous document  unige:34398  next document
add to browser collection
Title

Bimolecular Photoinduced Electron Transfer Beyond the Diffusion Limit: The Rehm–Weller Experiment Revisited with Femtosecond Time Resolution

Authors
Published in Journal of the American Chemical Society. 2014, vol. 136, no. 5, p. 2026-2032
Abstract To access the intrinsic, diffusion free, rate constant of bimolecular photoinduced electron transfer reactions, fluorescence quenching experiments have been performed with 14 donor/acceptor pairs, covering a driving-force range going from 0.6 to 2.4 eV, using steady-state and femtosecond time-resolved emission, and applying a diffusion-reaction model that accounts for the static and transient stages of the quenching for the analysis. The intrinsic electron transfer rate constants are up to 2 orders of magnitude larger than the diffusion rate constant in acetonitrile. Above ~1.5 eV, a slight decrease of the rate constant is observed, pointing to a much weaker Marcus inverted region than those reported for other types of electron transfer reactions, such as charge recombination. Despite this, the driving force dependence can be rationalized in terms of Marcus theory.
Identifiers
Full text
Article (Published version) (437 Kb) - document accessible for UNIGE members only Limited access to UNIGE
Other version: http://pubs.acs.org/doi/abs/10.1021/ja4118279
Structures
Research group Groupe Vauthey
Citation
(ISO format)
ROSSPEINTNER, Arnulf, ANGULO NUNEZ, Gonzalo Manuel, VAUTHEY, Eric. Bimolecular Photoinduced Electron Transfer Beyond the Diffusion Limit: The Rehm–Weller Experiment Revisited with Femtosecond Time Resolution. In: Journal of the American Chemical Society, 2014, vol. 136, n° 5, p. 2026-2032. https://archive-ouverte.unige.ch/unige:34398

235 hits

0 download

Update

Deposited on : 2014-02-21

Export document
Format :
Citation style :