Long-range excitons in conjugated polymers with ring torsions: poly(para-phenylene) and polyaniline

Abstract

Ring torsion effects on optical excitation properties in poly(para-phenylene) (PPP) and polyaniline (PAN) are investigated by extending the Shimoi-Abe model [Synth. Met. 78, 219 (1996)]. The model is solved by the intermediate exciton formalism. Long-range excitons are characterized, and the long-range component of the oscillator strengths is calculated. We find that ring torsions affect the long-range excitons in PAN more easily than in PPP, due to the larger torsion angle of PAN and the large number of bonds whose hopping integrals are modulated by torsions. Next, ring torsional disorder effects simulated by the Gaussian distribution function are analyzed. The long-range component of the total oscillator strengths after sample average is nearly independent of the disorder strength in the PPP case, while that of the PAN decreases easily as the disorder becomes stronger.