Accurate Description of Photoionization Dynamical Parameters.

Abstract

Calculation of dynamical parameters for photoionization requires an accurate description of the initial and final states of the system, as well as of the outgoing electron. We show that using a linear combination of atomic orbitals B-spline density functional theory (DFT) method to describe the outgoing electron, in combination with correlated equation of motion coupled cluster singles and double Dyson orbitals, gives good agreement with experiment and outperforms other simpler approaches, like plane and Coulomb waves, used to describe the photoelectron. Results are presented for cross-sections, angular distributions, and dichroic parameters in chiral molecules, as well as for photoionization from excited states. We also present a comparison with the results obtained using Hartree-Fock and DFT molecular orbitals selected according to Koopmans' theorem for the bound states.