Abstract
In contrast to decarboxylation from the ground electronic state, the 1( π, π ∗) excited 3-butenoic acid dissociates by C–O and C–C bond scissions, producing transient OH and HOCO radicals, respectively. The HOCO further dissociates to OH + CO. Laser-induced fluorescence (LIF) observation of OH showed the primary OH radical formation during 20 ns photolysis pulse, while the secondary OH radicals formed in ∼2 μs . Doppler spectroscopy showed that 36 kcal mol −1 relative translational energy released into C–O bond fission fragments. It appears that the dissociation occurs from the excited state potential energy surface.
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