Mapping potential energy surfaces by core electron excitation : the resonant Auger decay spectrum of BF3

International audienceHigh-resolution electron spectroscopy applied under resonant Auger-Raman conditions is shown to be a powerful tool for characterizing complex potential energy surfaces of core-excited states in polyatomic systems. BF3 is used as a prototype molecule: excitation of the B1s →2a2″ transition leads to an exceptional out-of-plane vibrational excitation resolved over a wide energy range (3.6 eV). The photon energy dependence of the spectra through the resonance profile is rationalized in the frame of the relative slopes of the potential energy curves along the boron out-of-plane displacement coordinate