Abstract
The fluorescence lifetime of trans-stilbene in dilute methylcyclohexane/ iso-hexane solution has been measured and the mean S 1 radiative ( k F), radiationless ( k I) and cis-isomerization ( k C) rate parameters have been determined from −90 to 60°C. S i consists of a fluorescent trans ( 1B u *) state ( k F 0 = 6.0 × 10 8 s −1) which undergoes reversible thermal-activated rotational internal conversion (Δ H = 1.75 kcal mole −1, Δ S = 10.6 cal deg −1 mole −1) to a non-fluorescent perp ( 1A g *) state. p( 1A g *) lies 610 cm −1 above t ( 1B u *) with an intermediate S 1 potential maximum. p( 1A g *) undergoes internal conversion( k I. ∞ = 5.8 × 10 8 s −1) to p ( 1A g) leading to cis-isomerization. This is the main isomerization channel over the whole temperature range.
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