Nonadiabatic effects in photoelectron spectra of HCl and DCl. I. Experiment

The HCl inner-valence photoelectron band at 26 eV binding energy has been recorded at high resolution. Discrete peaks arising from at least two separate vibrational progressions are superimposed on the broad continuum. Fano profiles are visible in one of the progressions. This indicates interference between superimposed electronic states, where weak avoided crossing allows two adiabatic states to couple. In the isotopic DCl molecular spectrum, the discrete lines are less pronounced, due to slower dissociation and therefore less coupling between the continuum and the bound state.