Modulating hydrogen bonding through Lewis acid complexation

Present calculations reveal that complexation with a Lewis acid such as BH 3 dramatically increases the strength of hydrogen bonding between H 2 O, H 2 S, HF, HCl, and NH 3 dimers. The increase in strength is attributed to the increase in electrostatic component. The interaction energies were found to increase by two to three folds (more than 50% increase in interaction energies). Detailed electronic structure analyses within the realm of quantum theory of atoms in molecules and non‐covalent interaction index confirms the strengthening of hydrogen bonding due to Lewis acid complexation. Decomposition of interaction energies using symmetry adapted perturbation theory reveals that the increase in interaction energy (more than 60%) is due to the dramatic increase in electrostatic component.