Resonance Raman cross‐section and polarization of light scattered from trans‐polyacetylene

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Abstract
The resonance excitation profile for the CC stretch mode of trans‐polyacetylene has been measured between 1.55 and 3 eV. For the main vibrational line at 1460 cm−1 a resonance enhancement of two orders of magnitude was observed for excitation with 1.7 eV. The peak position of the resonance shifted to higher values for a Raman shift larger than 1460 cm−1. The relationship between this position and the Raman shift was found to be different from that between the excitation energy and the satellite peak position. Experimental results have been compared with calculations from the particle in the box model for interrupted conjugations. Semiquantitative agreement was obtained for the various Raman shifts. The difference between the behaviour of the resonance peak and the satellite peak is shown to result from the influence of the distribution function and the lineshape function. The depolarization ratio for the CC stretch mode was observed to be 0.6, which is larger than expected for a randomly oriented anisotropic scatterer. However, it is in agreement with a situation where the scatterer is randomly oriented within one plane.

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