The four-component two-particle propagator for the calculation of double ionization spectra and elektron decay processes of systems with heavy elements

• Applicant: Privatdozent Dr. Markus Pernpointner
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2008 to 2012
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 73336379

The experimental measurement and theoretical description of double ionization processes and electronic decay mechanisms is an intensive field of research. Whereas considerable insight in the mechanisms could already be gained for light molecules the current methodology is inadequate for the correct description of heavy systems due to the strong interplay of relativistic effects and electron correlation. We therefore set out from the two-particle propagator in the fully four-component framework together with a two-hole population analysis which is able to provide detailed spectral information and final state characterization for the doubly ionized species. This new method treats scalar relativistic, spin-orbit and electron correlation effects on a consistent basis and will be applied to rare gas and hevay metal/rare gas clusters, halogen compounds and iodine-containing molecules. Unresolved experimental issues will hereby be clarified and the effect of relativity on electronic decay processes such as intermolecular Coulombic decay studied in detail. Together with the already available four-component one-particle propagator the new method will provide a powerful tool for the computation of double ionization spectra of heavy systems not accessible so far.

• DFG Programme: Research Grants