Multi-electron excitation contributions towards primary and satellite states in the photoelectron spectrum

The computation of Dyson orbitals and corresponding ionization energies has been implemented within the equation of motion coupled cluster singles, doubles and perturbative triples (EOM-CC3) method. Coupled to an accurate description of the electronic continuum via a time-dependent density functional approach using a multicentric B-spline basis, this yields highly accurate photoionization dynamical parameters (cross-sections, branching ratios, asymmetry parameters and dichroic coefficients) for primary (1h) states as well as satellite states of (2h1p) character. Illustrative results are presented for the molecular systems H2O, H2S, CS, CS2 and (S)-propylene oxide (a.k.a. methyloxirane).

Automated summary

In this study, the computation of Dyson orbitals and ionization energies using the EOM-CC3 method, coupled with a time-dependent density functional approach, has been implemented. The results provide accurate photoionization dynamical parameters for both primary and satellite states.