Photoabsorption and photoionization of the valence and inner (P 2p, 2s) shells of PF 3: Absolute oscillator strengths and dipole-induced breakdown pathways

Abstract

Absolute photoabsorption oscillator strengths (cross sections) for the valence and inner (P 2p, 2s) shells of phosphorus trifluoride (PF 3) have been measured using dipole ( e, e) spectroscopy in the 5–300 eV equivalent photon energy region (1 eV FWHM). The discrete spectral structures in the valence region and in the vicinity of the phosphorus 2p inner shell have also been studied at higher resolution (0.05 and 0.1 eV FWHM, respectively). Using these data and the S(−2) sum rule, the electric-dipole polarizability for PF 3 has been determined for the first time. In addition, dipole ( e, e+ion) coincidence spectroscopy has been used to obtain the photoionization efficiencies, photoion branching ratios, and absolute partial oscillator strengths for the molecular and dissociative photoionization channels of PF 3 from the first ionization threshold up to and above the phosphorus L shell edges to 175 eV. A consideration of the photoabsorption and photoionization measurement together with thermochemical data and results from previously published photoelectron branching ratios and photoelectron-photoion coincidence (PEPICO) studies provides information on the dipole-induced breakdown pathways of PF 3 in the photon region below 100 eV.