Journal of Chemical Physics, Vol.100, No.2, 1665-1672, 1994
Observation of 3 Resonances in the 3rd-Harmonic Generation Spectrum of Conjugated Polymers - Evidence for the 4-Level Essential States Model
Much of the theoretical effort to understand the mechanism of optical nonlinearity in pi-conjugated polymers has been focused towards explaining the early observation of only two resonances in the third harmonic generation spectrum of trans-polyacetylene. A recent theory of third order optical nonlinearity predicts three, instead of two, resonances, with their intensities decreasing with increasing frequencies. This is a fundamental difference between the band and the exciton pictures of pi-conjugated polymers. Very recent experimental results obtained with cis-polyacetylene, as well as earlier experiments on two blue forms of polydiacetylenes, are in complete agreement with this prediction. An isolated single strand of cis-polyacetylene should exhibit exciton behavior. We briefly discuss the latest experimental results for trans-polyacetylene.
Keywords:NONLINEAR OPTICAL SPECTROSCOPY;ONE-DIMENSIONAL EXCITONS;3RD-HARMONIC GENERATION;INFINITE POLYENES;POLYACETYLENE;POLYDIACETYLENE;SUSCEPTIBILITY;EXCITATIONS;FINITE