The generality of uncooperative and cooperative effects in elementary hydrogen-bonded systems

Abstract: The cooperative effect plays a significant role in understanding the intermolecular donor-acceptor interactions of hydrogen bonds (H-bonds, D-H...A). Herein, using the benchmark method of high-precision ab initio, the well-known cooperative effect is reproduced in elementary H-bonded systems with different D and A atoms. That is, with the decreasing of intermolecular distance, the D-H bond length first increases and then decreases, while the H...A bond length decreases. On the contrary, when D and A are the same, as the intermolecular distance decreases, the D-H bond length decreases without increasing, which is referred to as the uncooperative effect. Further analyses conclude that compared to cooperative H-bonded systems, uncooperative systems at their respective equilibrium position have a larger core-valence bifurcation (CVB) index (>0.022) and lower binding energies (<0.25 eV), showing a clear linear inverse relationship related to H-bond strength. Therefore, the intermolecular non-H-bonding interactions are predicted to reflect the uncooperative characteristics, which is confirmed by high-precision ab initio calculations. These findings provide a direction for the comprehensive understanding of H-bonds.