Core-electron contributions to the magnetic response of molecules with heavy elements and their significance in aromaticity assessments

Abstract

This study delves into the magnetic response of core electrons and their influence on the global magnetic response of planar and three-dimensional systems containing heavy elements, employing the removing valence electron (RVE) approximation. We also explore electronic aromaticity indices to understand the potential role of core electrons on electron delocalization in the absence of an external perturbation. The study reveals that core electrons significantly contribute to the overall magnetic response, especially to the magnetic shielding, affecting the interpretation of aromaticity. In contrast, the calculation of the electronic aromaticity indices suggests a negligible participation of the core electrons on electron delocalization. Despite their widespread use, the study emphasizes caution in labeling systems as strongly aromatic based solely on shielding function computations. It is noteworthy to emphasize the limitations associated with each aromaticity criterion; particularly in the context of magnetic shielding function calculations, the core-electron effect contamination is undeniable. Hence, the integration of various criteria becomes imperative for attaining a comprehensive understanding of magnetic responses within complex systems.