Valence shell photoionization dynamics calculations for oriented PF3 molecules

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Abstract
Photoelectron angular distributions (PADs) from the ionization of fixed‐in‐space, oriented PF3 molecules have been computed using the CMS‐Xα method. These molecule frame distributions are richly structured and varied with a high harmonic content. Interference terms between odd‐ and even‐partial waves create orientation in the PAD, and in some instances such oriented PADs may undergo a dramatic inversion, or reversal of direction, at a shape resonance. This phenomenon is attributable to the rapid rise in scattering phase of a single resonant partial wave component. A previously observed reversal in the experimental PF3 à band correlated photoelectron–photofragment ion recoil direction can be understood in these terms. Good agreement is found between the experimental and calculated molecule frame anisotropy for ionization of the 4e orbital over a range of electron kinetic energies. The assignment of the à band is thereby clarified, and the presence of a 4e→ka1(σ*) shape resonance at ∼3 eV can be confirmed without the necessity to scan through the resonance energy. Other shape resonances in the range 0–25 eV are identified by the calculations; all are investigated and the resonant behavior is scrutinized with the assistance of continuum eigenchannel plots. In this manner different trapping mechanisms can be visualized and the localization of the continuum scattering functions related to virtual atomic and molecular orbitals embedded in the ionization continuum.