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Theoretical prediction of ionization/oxidation potentials in conjugated polymers

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Abstract

Various density functional theory (DFT) functionals and semiempirical techniques were used to predict the ionization potentials of selected conjugated polymers. Ionization potentials at infinite chain lengths were estimated using Meier fit on oligomer data. Calculated gas-phase ionization potentials with BHandH functional showed good correlation with the experimental data. The results from the semiempirical techniques do not compare as favorably as the ones obtained from DFT methods. The data fitting allowed us to estimate the size of “effective ionization length”, which spanned over 20–30 double bonds in the conjugated backbone of the polymer in question.

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Notes

  1. P3HT oligomers have alkyl groups in their structure and therefore the data for thiophene oligomers has been used as reference only. Nonetheless, presence of alkyl groups are not expected to have significant effect on gas phase ionization potential.

  2. CAM-B3LYP calculations had to be performed on a personal computer. Therefore, the calculations were carried out on polymers with relatively small repeat units due to limitations in computational resources.

  3. Calculated oligomer IPs sometimes increased with the increasing number of repeat units, which represented an unrealistic picture.

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Acknowledgments

This work was supported by ND EPSCoR and Department of Energy under award #DE-FG52-08NA28921.

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  1. Department of Chemistry and Molecular Biology, North Dakota State University, Fargo, ND, 58108, USA

    Muhammet E. Köse

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Correspondence to Muhammet E. Köse.

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Köse, M.E. Theoretical prediction of ionization/oxidation potentials in conjugated polymers. Theor Chem Acc 128, 157–164 (2011). https://doi.org/10.1007/s00214-010-0810-y

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