Photoelectron spectra of chlorofluoromethanes

The photoelectron spectra of CFCl3, CF2Cl2, and CF3Cl have been recorded using Hei and Heii excitation. The relative intensities of the systems show a marked dependence on the energy of exciting radiation. The predominantly fluorine localized electrons have a greater ionization cross section for high energy (Heii) radiation while those localized mainly near the chlorine atoms have a greater ionization cross section for the low energy radiation.The spectra were assigned down to 25 eV on the basis of mutual comparison and by correlation with the assignments for chloro and fluoromethanes. The high resolution spectra revealed in some systems vibrational fine structure which is also discussed.