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

Integrated three-pulse stimulated echo peak shift data are compared for N,N-bis-dimethylphenyl-2,4,6,8-perylenetetracarbonyl diamide and $\mathrm{poly}[{2-(2}^{\prime }-\mathrm{ethylhexyloxy})-5-\mathrm{methoxy}-1,4-\mathrm{phenylenevinylene}]$ (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 oscillators 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.