Browsing by Subject "Poly-thiophene"

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    Effects of perfluorination on thiophene and pyrrole oligomers
    (2010) Salzner, U.
    The effect of perfluorination on thiophene and pyrrole oligomers in neutral, cationic, and anionic states was investigated with density functional theory at the (TD)B3P86-30%/6-31G* level. For the title compounds fluorination leads to planarization. For pyrroles a band gap reduction of 0.58 eV results, as unsubstituted pyrroles are nonplanar and disordered in the solid state. For thiophene the band gap is slightly increased as long thiophene oligomers are almost planar. Ionization energies and electron affinities increase upon fluorination by 0.65 and 0.60 eV for polythiophene and by 0.45 and 0.90 eV for polypyrrole. Conduction band widths increase by 0.5 for polythiophene and by 0.7 eV for polypyrrole. Spectra of charged (doped) forms are almost identical to those of the parent systems. Like parent systems, fluorinated oligomers with chain lengths of more than six rings develop a third UV absorption that increases in strength and decreases in energy upon chain length increase.
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    Investigation of charge carriers in doped thiophene oligomers through theoretical modeling of their UV/Vis spectra
    (2008) Salzner, U.
    The nature of the charge carriers in conducting organic polymers (COPs) is a long standing problem. Polythiophene is one of the prototypes of COPs and intensively studied. Because doping leads to changes in UV/vis spectra that are characteristic of the absorbing species, UV/vis spectra of charged thiophene oligomers with up to 25 rings were calculated with time-dependent density functional theory. The credibility of the method was established by comparing the results with a variety of theoretical levels and with experiment. Effects due to counterions (Cl3-) and solvent (CH 2Cl2) were examined. It was found that TDDFT employing hybrid functionals is accurate enough to distinguish the absorbing species. The findings offer an explanation for the experimentally observed difference in UV-spectra of medium-sized and long oligomers upon doping. As chain lengths of the oligomers increase and energy levels get closer, configuration interaction leads to additional absorption peaks in the high energy sub-band region (at around 1.5-2.5 eV). Thus, long oligomers do not behave differently from medium-sized ones upon doping, only their spectra are different. At low doping levels radical cations (polarons) are produced. At higher doping levels, dications that harbor weakly interacting polaron pairs are formed. Bipolarons are predicted only on very short chains or at high doping levels. There is no bipolaron binding energy and disproportionation of monocations into dications and neutral species is energetically unfavorable. © 2008 American Chemical Society.