The unusual stability of H‐bonded complexes in solvent caused by greater solvation energy of complex compared to those of isolated fragments

Here, the effect of solvent on the stability of non‐covalent complexes, was studied. These complexes were from previously published S22, S66, and X40 datasets, which include hydrogen‐, halogen‐ and dispersion‐bonded complexes. It was shown that the charge transfer in the complex determines whether the complex is stabilized or destabilized in solvent. The calculations of interaction and binding free energies, performed for all complexes of the S22, S66, and X40 datasets, confirm that most non‐covalent complexes destabilize in the solvent with respect to the gas phase. On the contrary, the hydrogen‐bond complexes with a sizable charge transfer are more stable in the solvent than in the gas phase.