Valence shell photoionization energies and cross-sections of NF3 and PF3

Relative outer valence shell ionization potentials and cross-sections were determined for the isostructural, Group 15, trifluorides NF3 and PF3 in the gas phase using synchrotron radiation. Excitation photon energies ranged from 70 to 160 eV. The experimental spectra were assigned and cross-sections analyzed with the aid of both MS-Xα and ab initio calculations. Spectral differences in peak energies and relative intensities are related to structural and electronic differences between these two fluoride molecules. Valence shell ionization potentials were compared to calculated values obtained by several different methods. The partial photoionization cross-sections for each orbital were obtained as a function of excitation energy and compared to theoretical results obtained with the Xα method