Abstract
First-principles density-functional theory (DFT) method has been used to investigate the structural and electronic properties of regioregular head-to-tail poly(3-hexylthiophene-2,5-diyl) (rrP3HT) crystal. Among the different configurations investigated for the rrP3HT crystal, the most stable is a staggered structure which is 875 meV/monomer more stable than isolated rrP3HT chains. Electronic properties of the rrP3HT crystal are strongly influenced by the magnitude of interactions that can be described by structural organization parameters such as the interchain distance in the stacking direction. From a disordered to a tightly packed polymer crystal, the direct band gap significantly decreases by , while the dispersion of highest occupied molecular-orbital and lowest unoccupied molecular-orbital bands increase by 0.60 and 1.33 eV, respectively.
1 More- Received 1 December 2008
DOI:https://doi.org/10.1103/PhysRevB.79.115207
©2009 American Physical Society