Absolute oscillator strengths for the photoabsorption, photoionization and ionic photofragmentation of phosphine. II. The P 2p and 2s inner shells

Abstract

Absolute photoabsorption oscillator strengths (cross sections) for the P 2p and 2s inner shells of phosphine have been obtained using dipole (e, e) spectroscopy in the equivalent photon energy range 120–220 eV. The respective contributions of the phosphine valence shell, P 2p and 2s oscillator strengths to the total absolute photoabsorption oscillator strengths have been estimated. The results are compared with previously published experimental and theoretical work for photoabsorption and photoionization of gaseous phosphine and for free P atoms in the P 2p and 2s regions. Dipole (e, e + ion) coincidence spectroscopy has been used to measure photoionization time-of-flight mass spectra at energies corresponding to resonant and Rydberg excitation as well as at selected energies in the P 2p and 2s photoionization continua of phosphine. Absolute photoionization oscillator strengths for the production of the molecular and dissociative (fragment) ions of phosphine have been obtained at these energies using the absolute photoabsorption oscillator strengths, the photoionization efficiency and the ionic photofragmentation branching ratios obtained from the mass spectra.