An ab initio study on boundaries for characterizing cooperative effect of hydrogen bonds by intermolecular compression

The cooperative effect plays a significant role in understanding the intermolecular donor-acceptor interactions of hydrogen bonds(H-bonds, D-H···A). Here, using the coupled-cluster singles and doubles with perturbative triple excitations(CCSD(T)) method of high-precision ab initio calculations, we show that the intermolecular H-bonded systems with different D and A atoms reproduce the structural changes predicted by the well-known cooperative effect upon intermolecular compression. That is, with decreasing intermolecular distance, the D-H bond length first increases and then decreases, while the H···A distance decreases. On the contrary, when D and A are the same, as the intermolecular distance decreases, the D-H bond length decreases without increasing. This obvious difference means that the cooperative effect may not be generally characterized by intermolecular compression. Interestingly, further analyses of many intermolecular systems confirm that this failure has boundaries, i.e., cooperative systems at their respective equilibrium positions have a smaller core-valence bifurcation(CVB) index(<0.022) and stronger binding energies(>0.25 eV), showing a clear linear inverse relationship related to H-bond strength. These findings provide an important reference for the comprehensive understanding of H-bonds and its calculation methods.