The SHEF1552 dataset: fundamental trends and physical insights into halogen, chalcogen, pnictogen and tetrel bonds

The Sigma-Hole Energies and additional Factors (SHEF1552) dataset, a comprehensive collection of 1,552 σ-hole interactions (halogen, chalcogen, pnictogen, and tetrel bonds) is introduced. Each complex, formed by pairing 82 σ-hole donors with 19 Lewis bases, was analysed using explicitly correlated coupled-cluster interaction energies and symmetry-adapted perturbation theory (SAPT). Analysis of this dataset identifies key geometric and energetic trends. Pnictogen bonds are, on average, the strongest interactions, followed by tetrel, chalcogen, and halogen bonds. The interaction energy-distance relationship exhibits a distinct boomerang-like distribution, defining two regimes of contact strength. Geometrically, while halogen, chalcogen, and tetrel bonds require σ-hole angles approaching 180◦ for short contacts, pnictogen bonds are unique, displaying no requirement for linearity at short distances. Additionally, roughly 5% of the complexes exhibit appreciable interaction energies despite intermolecular distances exceeding the sum of their van der Waals radii, confirming that strict distance cut-offs are overly restrictive. Finally, SAPT analysis shows the strongest σ-hole interactions are electrostatically dominated, whereas the weakest are primarily dispersion-driven. Beyond these physical insights, the SHEF1552 dataset can serve as a wide-ranging computational benchmark for geometries and energies of σ-hole interactions.