Contribution of the transition moments, form of the absorption band, exciton, and the correlation effects in the linear and nonlinear optical properties of conjugated polymers

Abstract This work compares the linear and nonlinear optical properties of polyenes and polyenynes. The simulation was made for finite and infinite conjugation of conjugated polymers, such as polyacetylene, β-carotene, bis (p-toluene sulfonate) (PTS) polyenyne, and a short conjugated polyenyne poly-2,6-decadyin-1,6-ylene azelate (PHDAz). The resonance energy and degree of conjugation are determined by fitting the linear absorption spectra. These parameters are then used for calculating the two photon and third-order nonlinear optical properties. The contribution of the transition moment, the form of the absorption band, the exciton, and phonons in the optical properties are determined. The difference of the experimental values is assigned to correlation effects. We found that the exciton, the correlation effects, and the conduction band are more important in the optical properties of polyenynes than of polyenes. In this way, the dependence of the optical properties of polyenynes on the conduction band makes it possible to increase their nonlinear optical properties by interaction with photons (θ ≈ 0). The dependence of the optical properties on the conduction band also produces that the finiteness of the conjugation strongly decreases the optical properties of polyenynes in relation to polyenes with similar conjugation. On the other hand, the phonons are more important in the optical properties of polyenes than of polyenynes. Consequently, the band is indirect for the studied polyenes and direct for the polyenynes. Therefore, the nonlinear optical properties in the resonance frequency of polyenyne PTS are higher than those for polyacetylene. We also found that asymmetric oscillations of χ(3) in the Brillouin zone increases the χ(3) final value in polyenynes. In addition, we found a change of sign of the wave function coefficients by the Peierls distortion of polyenes to become polyenynes, but this change of sign does not affect the optical properties. As a corollary, relaxation times for these conjugated polymers are estimated and compared to experimental data.