Abstract
The time-resolved resonance Raman (TR 3) spectrum of S 1 cis-stilbene in n-hexane is presented. Raman bands are observed at 243, 475, 742, 977, 1200 and 1440 cm −1. Their positions and relative intensities suggest that these belong to a high-order overtone progression (up to the fifth order) originating from the 243 cm −1 fundamental. This observation implies a large difference between S 1 and the resonant S n states in the equilibrium nuclear coordinate corresponding to the 243 cm −1 mode, with displacement Δ ∼ 12. Ground and excited state equilibrium geometries and frequencies are determined using ab initio molecular orbital calculations.
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