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WIREs Comput Mol Sci
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Electronic structure of conducting organic polymers: insights from time‐dependent density functional theory

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Conducting organic polymers (COPs) became an active field of research after it was discovered how thin films rather than insoluble infusible powders can be produced. The combination of the properties of plastics with those of semiconductors opened the research field of organic electronics. COPs share many electronic properties with inorganic semiconductors, but there are also major differences, e.g., the nature of the charge carriers and the amount of the exciton binding energy. Theoretical analysis has been used to interpret experimental observations early on. The polaron model that was developed from one‐electron theories is still the most widely used concept. In the 1990s, time‐dependent density functional theory (TDDFT) became available for routine calculations. Using TDDFT, electronic states of long oligomers can be calculated. Now UV spectra of neutral and oxidized or reduced species can be compared with in situ UV spectra recorded during doping. Likewise states of cations can be used to model photoelectron spectra. Analysis of states has resolved several puzzles which cannot be understood with the polaron model, e.g., the origin of the dual absorption band of green polymers and the origin of a ‘vestigial neutral band’ upon doping of long oligomers. DFT calculations also established that defect localization is not crucial for spectral changes observed during doping and that there are no bound bipolarons in COPs. WIREs Comput Mol Sci 2014, 4:601–622. doi: 10.1002/wcms.1194 This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Density Functional Theory Theoretical and Physical Chemistry > Spectroscopy
Structures of typical COPs.
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Cation spectra of 19‐FU at B3P86‐30%/6‐31G*and wB97XD/6‐31G* in gas phase and in CH2Cl2.
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Development of UV spectra of oligomers with increasing chain length.
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UV spectra of 6‐TH, and 6‐TH+ without (vertical) and with optimization of the cation structure.
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Bond‐length differences between of 19‐FU neutral form and cation in gas phase and in CH2Cl2 at B3P86‐30%/6‐31G* and wB97XD/6‐31G*.
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Defects caused by free radicals and charges in COPs.
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TDB3P86‐30%/6‐31G* UV spectra of donor–acceptor systems with 24 conjugated double bonds.
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UV spectra of 2‐BT through 12‐BT at B3P86‐30%/6‐31G*.
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Vibronically resolved main absorption peak of C12H14 at wB97XD/6‐31G*. The dark blue line indicates the vertical excitation; the light blue line represents the adiabatic excitation energy; and the red line denotes the experimental value from Ref .
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Twenty occupied and 10 unoccupied molecular orbital energies of systems with 24 conjugated double bonds: 12‐TH, 12‐BT, 4‐TH‐PYPY‐TH, 4‐PY‐PYPY‐PY, 4‐TH‐BT‐TH, 4‐EDOT‐BT‐EDOT, 4‐PY‐BT‐PY, and 3‐EDOT‐CDM‐EDOT at wB97XD/6‐31G*.
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Gas‐phase IPs (red), orbital energies (green), and ion‐state energies (blue) of 8‐thiophene.
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Structures of donor–acceptor systems.
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Theoretical and Physical Chemistry > Spectroscopy
Structure and Mechanism > Computational Materials Science
Electronic Structure Theory > Density Functional Theory

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