Nonlinear Optics of Linear Conjugated Polymers

The third order nonlinear optical properties of conjugated polymers have been considered promising since the 1970s when Sauteret et al reported large non-resonant values in PTS.[1] Although it is well-understood that the physical origin of the nonlinearities is due to the delocalization of the π-electrons, the details, and how best to calculate them have been the focus of a continuing theoretical dialogue. Until recently, experimental investigations of nonlinearities have been limited to only a few wavelengths. Now third harmonic generation (THG), which accesses only the electronic nonlinearities, can be performed over wide spectral ranges, for example from 500 to 2000 nm. The resulting third harmonic wavelength typically spans the electronic molecular transitions associated with the nonlinearities. By measuring the spectral distribution of both the amplitude and phase of the third harmonic signal, the dominant transitions (between the“essential states”) contributing to the nonlinearity can be identified. Such information is most useful for comparing with theories in which the oscillator strengths (transition dipole moments) for the various molecular transitions are calculated.