TY  - JOUR
A1  - Sutton, Christopher
A1  - Körzdörfer, Thomas
A1  - Gray, Matthew T.
A1  - Brunsfeld, Max
A1  - Parrish, Robert M.
A1  - Sherrill, C. David
A1  - Sears, John S.
A1  - Bredas, Jean-Luc
T1  - Accurate description of torsion potentials in conjugated polymers using density functionals with reduced self-interaction error
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - We investigate the torsion potentials in two prototypical pi-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.
Y1  - 2014
U6  - https://doi.org/10.1063/1.4863218
SN  - 0021-9606
SN  - 1089-7690
VL  - 140
IS  - 5
PB  - American Institute of Physics
CY  - Melville
ER  -