The ground and triplet excited states of cycloheptenone, cyclohexenone, and cyclopentenone have been studied using CASSCF calculations. For these three molecules, the difference in energy (DeltaE) between the twisted T(1) (3)(pi-pi*) minimum and T(1) (3)(pi-pi*)/S(0) intersection increases as the flexibility of the ring decreases. A strong positive correlation between DeltaE and the natural logarithm of the experimentally determined triplet lifetimes (ln tau) is found, suggesting that DeltaE predominantly determines the relative radiationless decay rates of T(1).