The vibrational progressions of the N→V electronic transition of ethylene:: A test case for the computation of Franck-Condon factors of highly flexible photoexcited molecules

The vibrational progressions of the N -> V electronic transition of ethylene-a test case for the computation of Franck-Condon factors between electronic states exhibiting very different equilibrium geometries-have been calculated by using both the Cartesian and the curvilinear internal coordinate representations of the normal modes of vibration. The comparison of the theoretical spectra with the experimental one shows that the Cartesian representation yields vibrational progressions which are not observed in the experimental spectrum, whereas the curvilinear one gives a very satisfying agreement, even in harmonic approximation. (c) 2006 American Institute of Physics.