Bond-distance-dependent decay probability of the N 1s → π* core-excited state in N2

We report the observation of the unusually weak decay of the N 1s --> pi* core-excited N-2 molecule to the (B) over tilde (2)Sigma(u)(+) final state of N-2(+), which is only detectable in an experiment with high sensitivity. The resonant Auger spectra exhibit an unexpected dependence on the selected vibrational level of the intermediate state. Theoretical calculations show that the interference between direct and resonant photoemission as well as a strong geometry dependence of the decay probability on the bond distance give rise to the observed features.