Bimolecular photoinduced electron transfer in non-polar solvents beyond the diffusion limit

Christoph Nançoz, Christopher Rumble, Arnulf Rosspeintner, Eric Vauthey

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12 Scopus citations


Electron transfer (ET) quenching dynamics in non-polar solvents are investigated using ultrafast spectroscopy with a series of six fluorophore/quencher pairs, covering a driving force range of more than 1.3 eV. The intrinsic ET rate constants, k0, deduced from the quenching dynamics in the static regime, are of the order of 1012-1013 M-1 s-1, i.e., at least as large as in acetonitrile, and do not exhibit any marked dependence on the driving force. A combination of transient electronic and vibrational absorption spectroscopy measurements reveals that the primary product of static quenching is a strongly coupled exciplex that decays within a few picoseconds. More weakly coupled exciplexes with a longer lifetime are generated subsequently, during the dynamic, diffusion-controlled, stage of the quenching. The results suggest that static ET quenching in non-polar solvents should be viewed as an internal conversion from a locally excited state to a charge-transfer state of a supermolecule rather than as a non-adiabatic ET process.

Original languageEnglish (US)
Article number244501
JournalJournal of Chemical Physics
Issue number24
StatePublished - Jun 28 2020

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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