Decoding Shake-up Satellites in XPS through Large-Scale ab initio Simulations: Spectral Signatures of Ring Fusion in Porphyrins

Abstract: In X-ray photoelectron spectroscopy (XPS), shake-up satellites arise when core ionization is accompanied by simultaneous charge-neutral valence excitations. Although these satellites can contain detailed structural information, they are rarely interpreted due to the lack of accurate and scalable theoretical methods. Here, we develop and apply a many-body perturbation theory framework within the $GW$ plus cumulant ($GW+C$) approach that enables accurate predictions of shake-up satellites in large molecular systems. For unfused, mono-fused, and doubly fused porphyrin derivatives with up to 170 atoms, we achieve excellent agreement with experiment, reproducing both main photoionization signals and satellite features within $0.2-0.3$ eV. We show that ring fusion strongly affects satellite features, whereas the N 1s photoionization signals remain unchanged. Our calculations reveal the mechanism behind these changes, identifying the spatial localization of valence excitations as the driving force. This work not only deepens understanding of the shake-up mechanism in porphyrins but also shows how predictive computations can unlock the chemical information encoded in satellites.