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

Abstract

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).

On the characteristic features of ionization in QED environments

“…Ionization is a key process in chemistry, as electron removal is used to characterize molecular systems in spectroscopic techniques such as the X-ray photoelectron spectroscopy 38 (XPS), or to follow the advancement of a chemical reaction. [39][40][41][42] Additionally, molecular ionization can be used to initiate and promote new reactive pathways. 43,44 In some recent papers, DePrince, 45 Liebenthal et al 46 and Pavovsevic et al 33,35 demonstrated that ionization potentials and electronic affinities change inside optical cavities.…”