PHOTOELECTRON AND RESONANCE P(LVV) AUGER-ELECTRON SPECTRA OF GAS-PHASE PF3 EXCITED BY SYNCHROTRON RADIATION

The photoelectron spectra and the resonance P(LVV) Auger spectra of PF3 were measured with monochromatized synchrotron radiation. The binding energies and the relative intensities of the molecular orbitals were obtained by curve fitting of the spectra. In addition the spin-orbit splitting of the P2p level in PF3 has been determined. The relative intensities of the 2a1 and 4a1 molecular orbitals show clearly the autoionization emission excited by a photon energy of 136.6 eV. Furthermore, the 2a1 photoelectron line shifts about 0.1 eV to a higher binding energy at this photon energy, and a weak spectral structure appears on the high binding energy side of the 4a1 photoelectron line. These lines are caused by the very fast dissociation of the molecule followed by autoionization of the excited state in fragments. The kinetic energies of the P(LVV) Auger lines in the resonant excitation are found to be about 8 eV larger than the energies of the spectral lines in the normal Auger spectrum. The photon energy 136.6 eV causes the excitation of the electron from the P2p1/2 level to the unoccupied sigma* orbital. The resonantly excited state seems to decay mainly through the spectator Auger process or through the autoionization emission.