Origin of line broadening in the electronic absorption spectra of conjugated polymers: Three-pulse-echo studies of MEH-PPV in toluene

Gregory D. Scholes, Delmar S. Larsen, Graham R. Fleming, Gary Rumbles, Paul L. Burn

Research output: Contribution to journalArticle

77 Citations (Scopus)

Abstract

Integrated three-pulse stimulated echo peak shift data are compared for N,N-bis-dimethylphenyl-2,4,6,8-perylenetetracarbonyl diamide and poly[2-(2′-ethylhexyloxy)-5-methoxy-1,4-phenylenevinylene] (MEH-PPV) in toluene solvent. These two molecules represent a model probe of solvation dynamics and a prototypical soluble, electroluminescent conjugated polymer, respectively. The results indicate that it is inappropriate to describe the linear absorption spectrum of MEH-PPV as being primarily inhomogeneously broadened. Conformational disorder along the polymer backbone gives rise to an ensemble of polyene electronic oscillator's that are strongly coupled to each other. As a consequence, fluctuations in the electronic energy gap on a time-scale of 50-fs derive primarily from bath-mediated exciton scattering. The data reported here provide an explanation for the broad, structureless electronic absorption of MEH-PPV. This interpretation provides a valuable insight into the nature of the initial photoexcited state, and the efficient population of the emissive state.

Original languageEnglish
Pages (from-to)13670-13678
Number of pages9
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume61
Issue number20
Publication statusPublished - May 15 2000

Fingerprint

Conjugated polymers
Solvation
Toluene
Excitons
electronic spectra
toluene
Absorption spectra
echoes
Energy gap
Scattering
absorption spectra
Molecules
polymers
Polymers
pulses
electronics
Diamide
Polyenes
solvation
baths

ASJC Scopus subject areas

  • Condensed Matter Physics

Cite this

Origin of line broadening in the electronic absorption spectra of conjugated polymers : Three-pulse-echo studies of MEH-PPV in toluene. / Scholes, Gregory D.; Larsen, Delmar S.; Fleming, Graham R.; Rumbles, Gary; Burn, Paul L.

In: Physical Review B - Condensed Matter and Materials Physics, Vol. 61, No. 20, 15.05.2000, p. 13670-13678.

Research output: Contribution to journalArticle

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AB - Integrated three-pulse stimulated echo peak shift data are compared for N,N-bis-dimethylphenyl-2,4,6,8-perylenetetracarbonyl diamide and poly[2-(2′-ethylhexyloxy)-5-methoxy-1,4-phenylenevinylene] (MEH-PPV) in toluene solvent. These two molecules represent a model probe of solvation dynamics and a prototypical soluble, electroluminescent conjugated polymer, respectively. The results indicate that it is inappropriate to describe the linear absorption spectrum of MEH-PPV as being primarily inhomogeneously broadened. Conformational disorder along the polymer backbone gives rise to an ensemble of polyene electronic oscillator's that are strongly coupled to each other. As a consequence, fluctuations in the electronic energy gap on a time-scale of 50-fs derive primarily from bath-mediated exciton scattering. The data reported here provide an explanation for the broad, structureless electronic absorption of MEH-PPV. This interpretation provides a valuable insight into the nature of the initial photoexcited state, and the efficient population of the emissive state.

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