Vibrationally resolved photoionization dynamics of CF4 in the DA12 state

Vibrationally resolved photoelectron spectroscopy of the CF4+ (DA12) state is studied for the first time over an extended energy range, 26.5⩽hν⩽50eV. It is found that the energy dependence of the totally symmetric stretching vibration is qualitatively different from all of the other vibrational modes. Moreover, the vibrational branching ratio curves for all of the symmetry forbidden vibrations are nearly identical. Qualitative arguments are used to show that it is likely that at least two shape resonances are present in the continuum, and that their characteristics, such as energy dependence and spatial localization, are distinctly different.