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Accurate description of torsion potentials in conjugated polymers using density functionals with reduced
Christopher Sutton1, Thomas Körzdörfer1, Matthew T Gray1
1School of Chemistry and Biochemistry and Center for Computational Molecular Science and Technology, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.
We quantified delocalization error in polymers using density functional theory. Correcting this error improves predictions of polymer structure and properties, like torsion barriers and conjugation length.
Area of Science:
- Computational Chemistry
- Materials Science
- Polymer Physics
Background:
- Density functional theory (DFT) is crucial for studying polymer properties.
- Semilocal and hybrid functionals exhibit delocalization errors affecting accuracy.
- Understanding these errors is key to reliable polymer simulations.
Purpose of the Study:
- To quantitatively analyze torsion potentials in polyacetylene and polydiacetylene.
- To assess the impact of delocalization error on polymer properties.
- To investigate the effectiveness of advanced DFT functionals.
Main Methods:
- Utilizing various flavors of density functional theory (DFT).
- Evaluating many-electron self-interaction error (MESIE) for fractional electron numbers.
- Employing non-empirically tuned long-range corrected hybrid functionals.
Main Results:
- Established a direct link between MESIE and errors in torsion barriers.
- Demonstrated significant MESIE reduction with advanced functionals.
- Achieved improved accuracy in describing torsion barrier heights.
Conclusions:
- Advanced DFT functionals offer a more accurate description of polymer torsion potentials.
- The MESIE is a reliable metric for quantifying delocalization errors.
- This approach enables accurate determination of effective conjugation length.
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