Calculation of resonance Raman excitation profiles for soluble and solid trans-polyacetylene

On the basis of previously developed theory, a quantitative analysis of the experimental data for sliced RREPs of soluble and solid trans-PA is undertaken. The effect of inhomogeneous environmental broadening of RREPs of a solute molecule due to the solvent–molecule interactions and of molecules in the solid due to differences in chain lengths is investigated. The role of the diagonal and non-diagonal terms of the scattering matrix is discussed. The method is applied to the analysis of experimental data of Cataliotti et al. for soluble trans-PA (R.S. Cataliotti, G. Paliani, G. Dellepiane, S. Fuso, S. Destri, L. Piseri, R. Tubino, J. Chem. Phys. 82 (1985) 2223) and of Lauchlan et al. for solid trans-PA (L. Lauchlan, S.P. Chen, S. Etemad, M. Kletter, A.J. Heeger, A.G. MacDiarmid, Phys. Rev. B 27 (1983) 2301). In both cases the major contribution to the broadening of the RREPs comes from an inhomogeneous distribution of the electronic energies.