Hole localization in the Cl (2p)^-1 ionization of CCl₄

The Cl (2p)^-1 photoionization of CCl₄  can produce four ²P_1/2  and four²P_3/2 states of CCl₄⁺.  Each set of four states is nearly degenerate so that to describe a dissociative ionization experiment one can use either a coherent superposition of the states that are either localized or delocalized across the four Cl atoms.  Depending on the dynamics of the dissociation process, an experiment which measures the photoelectron in coincidence with the fragments would measure the molecular frame photoelectron angular distributions (MFPADs) that are characteristic of either localized or delocalized hole states.  We have computed the MFPADs for these two cases to understand the extent to which an experiment could determine the degree of hole localization.  We use the decoupling of the hole states on the different Cl atoms to simplify the calculation to a three channel calculation including only the three Cl (2p)^-1 hole states on one atom.  Additionally we use both the grid and basis-set  complex Kohn methods to assess the adequacy of the basis sets used.   Finally, we use a three channel basis-set complex Kohn calculation to predict the  MFPADs  that can be measured from localized and delocalized representations of this core ionization process.