A variable energy photoelectron study of the valence levels and I 4d core levels of CF3I

Abstract

Using monochromatized synchrotron radiation, gas phase photoelectron spectra of CF3I have been obtained between 21 and 100 eV photon energies. Experimental valence band branching ratios have been compared with theoretical branching ratios from MS-Xα calculations. The generally good agreement between experiment and theory confirms the orbital assignment: 4e<4a1<1a2∼3e<2e<3a1<1e∼2a1 <1a1, in order of increasing binding energy. In contrast to CF4, MS-Xα calculations predict two shape resonances for CF3I at 15.2 eV (e channel) and 17.2 eV (a1 channel). Experimentally, weak shape resonances are observed on e orbitals at ∼14 eV kinetic energy. The cross sections are very useful for correlating orbitals in CF3I with those of CF4. For example, the cross sections suggest that the 3e orbital in CF3I correlates with the 1t1 orbital rather than the 4t2 orbital in CF4. After the onset of the I 4d level at ∼57 eV, intershell coupling becomes important in enhancing valence band levels having high I 5p character such as the 4e orbital. The I 4d branching ratio from 66 to 110 eV is similar to the Xe 4d branching ratio in atomic Xe, indicating atomic-like behavior for the I 4d subshell.