On the strength of hydrogen bonding within water clusters on the coordination limit

Hydrogen bonds (HB) are arguably the most important noncovalent interactions in chemistry. We study herein how differences in connectivity alter the strength of HBs within water clusters of different sizes. We used for this purpose the interacting quantum atoms energy partition, which allows for the quantification of HB formation energies within a molecular cluster. We could expand our previously reported hierarchy of HB strength in these systems (Phys. Chem. Chem. Phys., 2016, 18, 19557) to include tetracoordinated monomers. Surprisingly, the HBs between tetracoordinated water molecules are not the strongest HBs despite the widespread occurrence of these motifs (e.g., in ice Ih). The strongest HBs within H2O clusters involve tricoordinated monomers. Nonetheless, HB tetracoordination is preferred in large water clusters because (a) it reduces HB anticooperativity associated with double HB donors and acceptors and (b) it results in a larger number of favorable interactions in the system. Finally, we also discuss (a) the importance of exchange‐correlation to discriminate among the different examined types of HBs within H2O clusters, (b) the use of the above‐mentioned scale to quickly assess the relative stability of different isomers of a given water cluster, and (c) how the findings of this research can be exploited to indagate about the formation of polymorphs in crystallography. Overall, we expect that this investigation will provide valuable insights into the subtle interplay of tri‐ and tetracoordination in HB donors and acceptors as well as the ensuing interaction energies within H2O clusters. We study how differences in connectivity alter the strength of hydrogen bonds (HBs) within water clusters of different sizes using the interacting quantum atoms energy partition. We found that the strongest HBs within H2O clusters involve tricoordinated monomers. Nonetheless, HB tetracoordination is preferred in large water clusters because it reduces HB anticooperativy associated with double HB donors and acceptors and it results in a larger number of favorable interactions in the system.