Theoretical and Computational Chemistry

On the Accurate Description of Photoionization Dynamical Parameters

Sonia Coriani Technical University of Denmark


Calculation of dynamical parameters for photoionization requires an accurate description
of both initial and final states of the system, as well as of the outgoing electron.
We here show, that using a linear combination of atomic orbitals (LCAO) B-spline density
functional (DFT) method to describe the outgoing electron, in combination with
correlated equation-of-motion coupled cluster singles and double (EOM-CCSD) 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 (HF) and density-functional theory
molecular orbitals selected according to Koopmans’ theorem for the bound states.


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Supplementary material

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CCDyson+B-SplineDFT SI