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note
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b) as an energy criterion to exciton dissociation. According to the authors, an optical excitation (exciton) can dissociate if the gain of electrostatic energy is sufficient to (1) stabilize separation of charge carriers, and (2) prevent their recombination within the Coulomb potential well. In eq 6 of the current report, we consider exciton dissociation to be a ID Onsager-like process where dissociation occurs on-chain in the oligomers if the energy difference between the exciton in a strong external field (first term) exceeds its Coulombic binding energy (second term).
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96
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In MTHF, low-temperature dielectric measurements by Richert et al. [Chem. Phys. Lett. 1993, 216, 223] taken below the solvent glass transition temperature have shown the dielectric constant increases from ∼1.4 at 298 K to ∼19 at 77 K. Maxwell's dispersion relationship, used in eq 6 to estimate the dielectric constant of MTHF, becomes less valid as the solvent temperature decreases. The effect of increasing the dielectric constant in eq 6 would be to reduce the exciton binding potential by an order of magnitude, making exciton dissociation more probable in the presence of an applied field.
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Richert1
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97
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note
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Delocalization length (∼5.2 Å) of 1 PV unit was calculated in CS Chem3D Ultra version 6.0 using CS MOPAC Pro with the AM1 Hamiltonian. The structure was highly planar (RMS deviation ∼0.005 Å). Distances were measured between the para-carbon opposite the vinyl group and the outermost vinyl carbon. The best estimate for the short molecular axis of 1 PV for this geometry is 2.6 Å.
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