Accurate description of torsion potentials in conjugated polymers using density functionals with reduced self-interaction error

Abstract

We investigate the torsion potentials in two prototypical π-conjugated polymers, polyacetylene and polydiacetylene, as a function of chain length using different flavors of density functional theory. Our study provides a quantitative analysis of the delocalization error in standard semilocal and hybrid density functionals and demonstrates how it can influence structural and thermodynamic properties. The delocalization error is quantified by evaluating the many-electron self-interaction error (MESIE) for fractional electron numbers, which allows us to establish a direct connection between the MESIE and the error in the torsion barriers. The use of non-empirically tuned long-range corrected hybrid functionals results in a very significant reduction of the MESIE and leads to an improved description of torsion barrier heights. In addition, we demonstrate how our analysis allows the determination of the effective conjugation length in polyacetylene and polydiacetylene chains.