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For the sake of simplicity, the term "polymer" is used in this work.
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84962435780
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The spectra are obtained by a superposition of Gaussian lineshape functions and thus do not explicitly contain vibronic progressions
-
The spectra are obtained by a superposition of Gaussian lineshape functions and thus do not explicitly contain vibronic progressions.
-
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54
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33846490219
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The linear relationship between the S1 energy and 1/n does not hold for very long chains as discussed in detail, e.g., in J. Gierschner, J. Cornil, H.-J. Egelhaaf, Adv. Mater. 2007, 19, 173.
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In this context it has to be kept in mind that for calculating the e-h wavefunctions the full excited state wavefunction is considered going beyond the uncorrelated single determinant picture derived from the dominant orbitals. In fact, one can show that the proper behavior of the exciton can only be obtained when considering the complete SCI-derived wavefunction, while the interaction within the e-h pair is not properly accounted for in a single-determinant picture based on standard orbitals
-
In this context it has to be kept in mind that for calculating the e-h wavefunctions the full excited state wavefunction is considered going beyond the uncorrelated single determinant picture derived from the dominant orbitals. In fact, one can show that the proper behavior of the exciton can only be obtained when considering the complete SCI-derived wavefunction, while the interaction within the e-h pair is not properly accounted for in a single-determinant picture based on standard orbitals.
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60
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84962383874
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At slightly higher energies a (weaker) optically allowed state concentrated in the left part of the molecule is found
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At slightly higher energies a (weaker) optically allowed state concentrated in the "left" part of the molecule is found.
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61
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An exception is the protonation of the terminal pyridine unit 4, which can even result in the lowest-lying state becoming nonemissive see the 3, 4 case in the ESI, This can, however be attributed to end-effects, i.e, a lone pyridine at the end of the chain, which on the one hand should have a relatively minor influence on the polymer spectra and, as discussed above, should actually not happen here, as there is usually a bromo atom attached to terminal pyridines. See also the corresponding remark in the ESI
-
An exception is the protonation of the terminal pyridine unit 4, which can even result in the lowest-lying state becoming nonemissive (see the "3, 4" case in the ESI). This can, however be attributed to "end-effects", i.e., a lone pyridine at the end of the chain, which on the one hand should have a relatively minor influence on the polymer spectra and, as discussed above, should actually not happen here, as there is usually a bromo atom attached to terminal pyridines. See also the corresponding remark in the ESI.
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- counter-ion are discussed in the ESI.
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Here no solvent effects were considered. Calculations including the solvent turned out to be primarily important for inducing the proton transfer from the chloride to the pyridine (see ref. [9c]).
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Here no solvent effects were considered. Calculations including the solvent turned out to be primarily important for inducing the proton transfer from the chloride to the pyridine (see ref. [9c]).
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