Albrecht theory of resonance Raman scattering: applied to conjugated polymers in the solid-state limit

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The connection between the vibronic picture of Raman scattering and the third-order perturbation approach in solid-state physics is clarified. Starting from the Kramers—Heisenberg—Dirac formula for Raman scattering, we derive analytical expressions for the Condon and Herzberg—Teller terms for polyacetylene in the solid-state limit. Close to resonance the Condon term dominates and converges to the usual solid-state result. In the off-resonance region the Herzberg—Teller term is comparable to the Condon term, in contrast to the small molecule case.