Rotational state dependence of radiationless transitions in S1 propynal

Bitto, H.; Willmott, P. R.; Huber, J. Robert
October 1991
Journal of Chemical Physics;10/1/1991, Vol. 95 Issue 7, p4765
Academic Journal
The rotational state dependence of the radiationless processes of S1 propynal, HC≡CCHO, was investigated in three selected vibronic bands located at an excess energy of about 3000 cm-1 in a molecular beam using molecular quantum beat spectroscopy. The number of quantum beat frequencies counted in single rovibronic fluorescence decays shows a clear dependence on the rotational quantum number N of the excited rovibronic singlet state, reflecting an increase of the number of coupling triplet states nT by a factor of 4, from N=0 to 14. This increase is accompanied by a lengthening of the decay lifetimes by a factor of 3. Given eigenstate resolution, the effect of magnetic interactions in the triplet state is discussed and it is concluded that the N dependence is predominantly due to mixing of K states resulting in a symmetry breakdown. This mixing is proposed to be mainly induced by hyperfine interaction via the dipole–dipole term.


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