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Volumn 18, Issue 21, 2008, Pages 3377-3385

Doped conductive polymers: Modeling of polythiophene with explicitly used counterions

Author keywords

[No Author keywords available]

Indexed keywords

ABS RESINS; BOND LENGTH; BOUNDARY VALUE PROBLEMS; CHARGE CARRIERS; CONDUCTIVE PLASTICS; DENSITY FUNCTIONAL THEORY; ELECTRONIC STRUCTURE; OPTICAL PROPERTIES; ORGANIC CONDUCTORS; ORGANIC POLYMERS; PHOTOTRANSISTORS; POLYMERS; PROBABILITY DENSITY FUNCTION; SEMICONDUCTOR DOPING; SULFUR COMPOUNDS; THIOPHENE;

EID: 55849145099     PISSN: 1616301X     EISSN: 16163028     Source Type: Journal    
DOI: 10.1002/adfm.200800639     Document Type: Article
Times cited : (38)

References (70)
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    • Early VEH calculations of highly doped conjugated polymers were performed on polymers without dopants using geometries of tetramers which were optimized with dopant. J. L. Brédas. B. Thémans, J. G. Fripiat, J. M. André, R. R. Chance. Phys. Rev. B 1984, 29, 6761
    • Early VEH calculations of highly doped conjugated polymers were performed on polymers without dopants using geometries of tetramers which were optimized with dopant. J. L. Brédas. B. Thémans, J. G. Fripiat, J. M. André, R. R. Chance. Phys. Rev. B 1984, 29, 6761.
  • 57
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    • Conformations in which the counterions were positioned between thiophene rings and in-plane with them can be considered. We did not study such conformations since the positioning of the counterions next to one of the thiophene rings allowed a more systematic study of the effect of dopant position. We note that the differences between different in-plane conformations for doped oligothiophenes are below 1.5kcal · mol 1 per Cl3 in favor of conformations in which the counterions were positioned between thiophene rings, 17
    • (17)
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    • 1 higher in energy than the inplane conformation.
    • 1 higher in energy than the inplane conformation.
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    • (11) estimation of polymer properties using PBC calculations are practically much faster than using oligomer extrapolation.
    • (11) estimation of polymer properties using PBC calculations are practically much faster than using oligomer extrapolation.
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    • We note that for short unit cells PBC calculation require significantly more computational time than the calculations of oligomers of similar size. However, only few k-points are required for PBC calculations which use long unit cell n, 20, and such calculations for polymers require similar computational time to that of oligomers
    • We note that for short unit cells PBC calculation require significantly more computational time than the calculations of oligomers of similar size. However, only few k-points are required for PBC calculations which use long unit cell (n = 20), and such calculations for polymers require similar computational time to that of oligomers.
  • 69
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    • When the C1-C2 and C3-C4 bonds of a thiophene ring are shorter than the C2-C3 bond (so producing a Λ-shaped pattern in the sets of three linked data points shown in Fig. 2, the ring is considered aromatic (left scheme, By contrast, when the C1-C2 and C3-C4 bonds of a thiophene ring are longer than the C2-C3 bond (thus producing a V-shaped pattern in the sets of three linked data points shown in the Fig. 2, the ring is considered quinoid right scheme
    • 2-C3 bond (thus producing a V-shaped pattern in the sets of three linked data points shown in the Fig. 2), the ring is considered quinoid (right scheme).
  • 70
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    • Although comparison of calculated mid-gaps with experimentally measured Vis-NIR spectra of doped polythiophene would be highly desirable, we believe that our calculated values, based on B3LYP/6-31G(d) calculated HOCO and LUCO energies can only be used for qualitative comparisons. Higher level calculations are required for quantitative comparison with experimental data
    • Although comparison of calculated mid-gaps with experimentally measured Vis-NIR spectra of doped polythiophene would be highly desirable, we believe that our calculated values, based on B3LYP/6-31G(d) calculated HOCO and LUCO energies can only be used for qualitative comparisons. Higher level calculations are required for quantitative comparison with experimental data.


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