The density functional theory was employed to study the structures, ionization potentials(IPs), electron affinities(EAs), and HOMO-LUMO gaps(ΔH-L) of the oligomers. The time-dependent density functional theory(TD-DFT) and ZINDO were employed to study the lowest excitation energies(Egs) and the absorption and emission spectra of the oligomers of polyfluorene(PF) and poly(fluorene-co-thiophene)(PFT). By extrapolating ΔH-L and Egs to those of infinite chain length, band gaps and effective conjugation lengths of the corresponding polymers were obtained. The IPs, EAs and λabs of the polymers were obtained by extrapolating those of the oligomers to the inverse chain length equal to zero(1/n=0). The outcome shows the decreased dihedral angle between fluorene and thiophene units in the PFT compared to that between fluorene units in the PF results in the increased efficient conju-gation of PFT. These cause both the maximal absorption and emission wavelengths of PFT redshifted compared with those of PF.
