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Article Dans Une Revue Journal of Molecular Spectroscopy Année : 2010

Centrifugaldistortionanalysis of the rotationalspectrum of aziridine: Comparison of differentHamiltonians

Résumé

Previous measurements of rotationalspectrum of aziridine up to 1.85 THz have been supplemented by new data in 225-660 GHz frequency range. A total of 1465 transitions (915 of them are newly assigned ones) with maximum values of J = 59 and Kc = 50 were fit to a standard Watson Hamiltonian using the S- and A-reductions and the representations Ir and IIIr. Although aziridine is an asymmetric oblate top, the combination (A, IIIr) gives the worst results. From the point of view of the convergence of the Hamiltonian, the best results are obtained with the combination (S, IIIr). It is explained that the failure of the combination (A, IIIr) is due to the large value of the parameter σ=(2C-A-B)/(A-B) which makes some sextic centrifugaldistortion constants much too large impeding the convergence of the Hamiltonian. It is also shown that the calculation of the centrifugaldistortion constants from a force field is sometimes an ill-conditioned operation. Finally, the use of a non-reduced Hamiltonian (with six quartic centrifugaldistortion constants) was successful in the particular case thanks to the method of predicate observations.

Dates et versions

hal-00757565 , version 1 (27-11-2012)

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Roman Motiyenko, Laurent Margulès, E. A. Alekseev, Jean-Claude Guillemin, Jean Demaison. Centrifugaldistortionanalysis of the rotationalspectrum of aziridine: Comparison of differentHamiltonians. Journal of Molecular Spectroscopy, 2010, 264 (2), pp.94-99. ⟨10.1016/j.jms.2010.09.007⟩. ⟨hal-00757565⟩
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