The computation of Dyson orbitals and corresponding ionization energies has been implemented within the Equation of Motion Coupled Cluster Singles, Doubles, and Perturbative Triples (EOMCC3) 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 states (1h) as well as satellite states of (2h-1p) character. Illustrative results are presented for the molecular systems H2O, H2S, CS, CS2 and (S)-propylene oxide (a.k.a. methyloxirane).
Multi-electron excitation contributions towards the primary and satellite states in the photoelectron spectrum. Supplementary Information