Coupling between the vibrational motion of core-excited and valence-ionized states of N2

Fluorescence emission of the N-2(+) (A (2)Pi(u)) and N-2(+) (B (2)Sigma(u)(+)) states has been investigated after resonant excitation of the N-2 (1S(-1)-pi*) resonance with monochromatized synchrotron radiation. The vibrational structure of the core-excited state as well as of the final ionic state has been resolved in the photoexcitation and in the dispersed fluorescence spectra, respectively. A detailed analysis of the experimental spectra and a comparison with theoretical results show a strong coupling between the vibrational levels in the core-excited and the ionic state produced via autoionization. The N-2(+) (A (2)Pi(u)) potential curve is almost parallel to the core-excited state which causes mainly (Delta v = 0) transitions in the autoionization process. For the N-2(+) (B (2)Sigma(u)(+)) state, the production via the pi* resonance leads to the population of higher vibrational states which are only very weakly populated by direct ionization. The calculations reproduce the observed structures and underline the complementary character of fluorescence and photoelectron spectroscopy.