Theory on polarization-averaged core-level molecular-frame photoelectron angular distributions: I. A Full-potential method and its application to dissociating carbon monoxide dication

TL;DR

This paper develops a full-potential multiple scattering theory to accurately model polarization-averaged molecular-frame photoelectron angular distributions from dissociating CO$^{2+}$, revealing detailed scattering images and bond-length-dependent shape changes.

Contribution

It introduces a full-potential method avoiding spherical harmonic expansion and incorporates RASPT2 for realistic core-hole effects, advancing theoretical analysis of PA-MFPADs.

Findings

Full-potential treatment is crucial at 100 eV for accurate PA-MFPADs.

PA-MFPADs are insensitive to the type of major excited state.

PA-MFPADs change shape significantly with C-O bond length.

Abstract

We present a theoretical study on polarization-averaged molecular-frame photoelectron angular distributions (PA-MFPADs) emitted from $1s$ orbital of oxygen atom of dissociating dicationic carbon monoxide CO$^{2+}$. Due to the polarization-average, contribution of direct wave of photoelectron which has the biggest contribution to MFPADs is removed, so that PA-MFPADs clearly show the detail of scattering image of the photoelectron. As a result, it is necessary to employ well precise theory for the continuum state for the theoretical analysis. In this study, we applied our Full-potential multiple scattering theory, where the space is partitioned by using Voronoi polyhedra and truncated spheres to take into account the electron charge density outside the physical atomic spheres. We did not use spherical harmonic expansion of the cell shape functions to avoid convergence problems.The potentials in scattering cells are prepared employing Multiconfigurational Second-Order Perturbation Theory Restricted Active Space (RASPT2) method in order to take into account the influence of core hole in the electron charge density in the final state to realize realistic relaxation. We showed that the Full-potential treatment plays an important role for the PA-MFPADs at 100 eV of kinetic energy of photoelectron. Instead, the PA-MFPADs are not sensitive to type of major excited state in the Auger final state.We also studied the dynamics of CO$^{2+}$ dissociation. We found that the PA-MFPADs dramatically change its shape as a function of C-O bond length.