title: Exciton localization in disordered poly(3-hexylthiophene).
abstract: Singlet exciton localization in conformationally disordered poly(3-hexylthiophene) (P3HT) is investigated via configuration interaction (singles) calculations of the Pariser-Parr-Pople model. The P3HT structures are generated by molecular dynamics simulations. The lowest-lying excitons are spatially localized, space filling, and nonoverlapping. These define spectroscopic segments or chromophores. The strong conformational disorder in P3HT causes breaks in the pi-conjugation. Depending on the relative values of the disorder-induced localization length and the distances between the pi-conjugation breaks, these breaks sometimes serve to pin the low-lying localized excitons. The exciton confinement also causes a local spectrum of low-lying exciton states. Coulomb-induced intra- or interchain interactions between spectroscopic segments in close spatial proximity can delocalize an exciton across these segments, in principle causing phase coherent transition dipole moments.
authors.affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, Oxford OX1 3QZ, United Kingdom. william.barford@chem.ox.ac.uk
authors.forename: William
authors.initials: W
authors.lastname: Barford
authors.forename: David G
authors.initials: DG
authors.lastname: Lidzey
authors.forename: Dmitry V
authors.initials: DV
authors.lastname: Makhov
authors.forename: Anthony J H
authors.initials: AJ
authors.lastname: Meijer