Competition between Halogen Bonding and π‐Hole Interactions Involving Various Donors: The Role of Dispersion Effects

In this study several σ‐ and π‐hole complexes between IF and pnicogen ZO₂F (Z=P, As), chalcogen ChO₃ (Ch=S, Se) and tetrel TrOF₂ (Tr=Si, Ge) ‐bearing compounds were optimized at the RI‐MP2/def2‐TZVPD level of theory. All complexes were characterized as minima by frequency analysis calculations. In addition, a comparative CCSD(T) and DFT (with and without dispersion correction) study using the BP86, B3LYP and M06‐2X method was done in order to analyze the role of dispersion effects in the σ‐/π‐hole binding. Finally the Bader’s AIM analysis of several complexes was performed to further characterize the interactions discussed herein.