THE ELECTRONIC-STRUCTURE OF TRIFLUOROPHOSPHINE STUDIED BY PHOTOELECTRON-SPECTROSCOPY WITH VARIABLE PHOTON ENERGY

The photoelectron spectrum of PF3 has been measured using synchrotron radiation. Relative partial photoionization cross-section and branching ratio data are reported for the valence bands (8-24 eV) over the photon-energy range 30-95 eV. Molecular orbitals regarded previously as purely fluorine lone pair in composition are shown to have significant phosphorus 3p character. Comparison of the results obtained on PF3 with those obtained previously on [Ni(PF3)4] shows that the complex molecular orbitals of the latter derived from the 5e orbitals of PF3 have some nickel 3d character. Metal-to-phosphorus back donation, proposed to occur through the 7e PF3 molecular orbitals, is thus shown also to involve the 5e.