Abstract
This work introduces the Coupled-Resonances (CR) line shape as a theoretically robust model for analyzing asymmetric peaks in photoelectron spectra, broadly applicable across various materials. The CR line shape extends the conventional Lorentzian distribution by incorporating an interference term that contributes to the peak asymmetry. This new approach addresses limitations of the widely used Doniach- Šunjić (D&S) model, which is often applied beyond its intended scope of metals with high densities of states at the Fermi level due to a lack of viable alternatives. Unlike the DS line shape, the CR model is integrable, enabling its use in precise chemical composition calculations, and it consistently provides superior fits to experimental data. The CR model's versatility is evident in its ability to simplify to a Lorentzian for a single resonance. However, with multiple resonance states, the total line shape is no longer a simple summation of individual peak contributions. Instead, a significant interference term emerges, profoundly contributing to the observed peak asymmetry and shifting the maximum peak intensity. This highlights the critical need to consider interference terms in multiplet calculations of lineshapes. The CR line shape has been implemented in the freely available software, AAnalyzer. While most asymmetric peaks are accurately described by CR Type-II (two resonances), some require CR Type-III (three resonances) for optimal fitting, as demonstrated in the included examples. Ultimately, the CR model offers a more accurate and versatile approach to analyzing asymmetric lineshapes in photoemission spectroscopy, with broad applicability to a wide range of materials, including metals.