jp071585n_si_001.pdf (68.3 kB)
Electric Field Effects on Internal Conversion: An Alternative Mechanism for Field-Induced Fluorescence Quenching of MEH-PPV and Its Oligomers in the Low Concentration Limit
journal contribution
posted on 2007-07-12, 00:00 authored by Timothy M. Smith, Jung Kim, Linda A. Peteanu, Jurjen WildemanIn a previously published study (J. Phys. Chem. B 2006, 110, 7732−7742), we reported field-induced
fluorescence quenching in both poly[2-methoxy,5-(2‘-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV)
and several model oligomers in solvent glass matrices at high dilution (<0.1% by weight). The observed
quenching is not readily explained by field-induced exciton dissociation or by the presence of free charges,
two mechanisms that have been invoked to explain this phenomenon by previous authors. A model is developed
here that ascribes the observed fluorescence quench in dilute samples to an energetic shift of the relaxed
excited state caused by the electric field resulting in increased nonradiative relaxation. To determine whether
the relevant nonradiative pathway is intersystem crossing or internal conversion, analytical expressions are
derived for each of these two mechanisms. Only the expression derived for the Stark effect on the rate of
internal conversion quantitatively predicts the magnitude of quench observed in MEH-PPV and in the oligomeric
species.
History
Usage metrics
Categories
Keywords
ConversionphenomenonOligomerdissociationsampleInternalnonradiative relaxationStark effectquenchingvinylenechargeexcitonpresencemechanismPhymodel oligomersElectric Field Effectsnonradiative pathwaydilutionFluorescenceglass matricesintersystemconversionChempolyoligomeric speciesAlternative MechanismfluorescenceshiftmagnitudeLow Concentration LimitInQuenchingexpression
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC