X‐Ray Photoelectron Spectroscopy as Useful Technique for the Quantification of Halogen and Chalcogen Bonding Interactions

This manuscript introduces a novel approach for quantifying the strength of halogen and chalcogen bonding interactions involving heavy elements of groups 17 (Br, I) and 16 (Se, Te). While X‐ray photoelectron spectroscopy (XPS) is a recognized diagnostic tool for halogen bonding, its application for characterizing chalcogen bonds, or quantifying the strength of either interaction via spectral shifts, remains unexplored. To current knowledge, this study is the first to propose and rigorously validate such an approach. A comprehensive benchmark investigation is first conducted to identify the most reliable theoretical methods for reproducing experimental XPS signals. Subsequently, a clear correlation between calculated XPS shifts and the interaction strength is established, demonstrating XPS as a novel and experimentally accessible method. This work aims to significantly advance the understanding and rational design of noncovalent interactions in supramolecular chemistry and materials science.