Absolute oscillator strengths for the valence and inner (P 2p,2s) shell photoabsorption, photoionization, and ionic photofragmentation of PF5

Absolute oscillator strengths (cross-sections) for the photoabsorption of phosphorus pentafluoride (PF,) have been measured for the first time in the valence and phosphorus 2p discrete regions using high-resolution (0.0-0.1 eV fwhm) dipole (e,e) spectroscopy. Long-range data (10-300 eV) have also been obtained at lower resolution (1 eV fwhm), from which the absolute oscillator strength scale has been determined using the valence-shell Thomas-Reiche-Kuhn sum-rule. The accuracy of the present measurements has been tested using the S(-2) sum rule normalization. Evaluation of the S(-2) sum using the presently reported absolute photoabsorption oscillator strength data gives a dipole polarizability for PF5 in good agreement with the experimental value. The photoionization efficiencies, photoion branching ratios, and absolute partial oscillator strengths for molecular and dissociative photoionization have also been determined for PF5 by dipole (e,e + ion) coincidence spectroscopy from the first ionization threshold up to and above the phosphorus 2p edge. (C) 1997 Elsevier Science B.V.