Abstract
The laser induced T1(nπ*)←S0 phosphorescence excitation spectrum of jet-cooled acetaldehyde has been observed for the first time with a rotating slit nozzle excitation system. The vibronic origins were fitted to a set of levels that were obtained from a Hamiltonian that employed flexible torsion-wagging large amplitude coordinates. The potential surface extracted from the fitting procedure yielded barriers to torsion and inversion of 609.68 and 869.02 cm−1, respectively. Minima in the potential hypersurface at θ=61.7° and α=42.2° defined the equilibrium positions for the torsion and wagging coordinates. A comparison to the corresponding S1-state parameters showed that the torsion barrier (in cm−1) does not greatly change, S1/T1=710.8/609.7, whereas the barrier height for the wagging-inversion barrier increases dramatically, 574.4/869.0.
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