Comment on “Exploring nature and predicting strength of hydrogen bonds: A correlation analysis between atoms‐in‐molecules descriptors, binding energies, and energy components of symmetry‐adapted perturbation theory”

Abstract We evaluate the correlation between binding energy (BE) and electron density ρ ( r ) at the bond critical point for 28 neutral hydrogen bonds, recently reported by Emamian and co‐workers ( J. Comput. Chem ., 2019 , 40 , 2868). As an efficient tool, we use local stretching force constant derived from the local vibrational mode theory of Konkoli and Cremer. We compare the physical nature of BE versus , and provide an important explanation for cases with significant deviation in the BE– relation as well as in the BE– ρ ( r ) correlation. We also show that care has to be taken when different hydrogen bond strength measures are compared. The BE is a cumulative hydrogen bond strength measure while is a local measure of hydrogen bond strength covering different aspects of bonding. A simplified and unified description of hydrogen bonding is not always possible and needs an in‐depth understanding of the systems involved.