Quantitative studies of the photoabsorption and photoionization of PCl3 in the valence and inner (P 2p,2s; Cl 2p,2s) shell regions Original Research Article

Electronic excitation spectra and absolute photoabsorption oscillator strengths (cross sections) have been measured in the vacuum ultraviolet and soft X-ray energy regions for the valence and inner (P 2p,2s; Cl 2p,2s) shell photoabsorption of phosphorus trichloride (PCl3) from 5 to 350 eV (1 eV fwhm) using dipole (e,e) spectroscopy. The discrete structures in the valence region and in the vicinity of the phosphorus 2p and chlorine 2p inner shells have also been studied at higher resolution (0.05–0.1 eV fwhm). Evaluation of the S(−2) sum using the presently reported absolute photoabsorption oscillator strength data gives a dipole polarizability for PCl3 within 1% of the experimental value. The photoionization efficiency, ionic photofragmentation branching ratios, and absolute partial oscillator strengths for molecular and dissociative photoionization have also been determined for PCl3 by dipole (e,e+ion) coincidence spectroscopy from the first ionization threshold up to the chlorine 2s edge.