Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Delegación Coyoacán C.P., 04510, CDMX, México.
Chemphyschem. 2021 Jun 16;22(12):1269-1285. doi: 10.1002/cphc.202000981. Epub 2021 May 17.
Non-additive effects in hydrogen bonds (HB) take place as a consequence of electronic charge transfers. Therefore, it is natural to expect cooperativity and anticooperativity in ion-water interactions. Nevertheless, investigations on this matter are scarce. This paper addresses the interactions of (i) the cations Li , Na , K , Be , Mg , and Ca together with (ii) the anions F , Cl , Br , NO and SO with water clusters (H O) , n=1-8, and the effects of these ions on the HBs within the complete molecular adducts. We used quantum chemical topology tools, specifically the quantum theory of atoms in molecules and the interacting quantum atoms energy partition to investigate non-additive effects among the interactions studied herein. Our results show a decrease on the interaction energy between ions and the first neighbouring water molecules with an increment of the coordination number. We also found strong cooperative effects in the interplay between HBs and ion-dipole interactions within the studied systems. Such cooperativity affects considerably the interactions among ions with their first and second solvation shells in aqueous environments. Overall, we believe this article provides valuable information about how ion-dipole contacts interact with each other and how they relate to other interactions, such as HBs, in the framework of non-additive effects in aqueous media.
氢键（HB）中的非加和效应是电子电荷转移的结果。因此，在离子-水相互作用中存在协同和反协同作用是很自然的。然而，对此类问题的研究还很少。本文研究了（i）阳离子 Li、Na、K、Be、Mg 和 Ca 以及（ii）阴离子 F、Cl、Br、NO 和 SO 与水分子簇（H2O），n=1-8 的相互作用，以及这些离子对完整分子加合物中氢键的影响。我们使用量子化学拓扑工具，特别是分子中的原子量子理论和相互作用量子原子能量分区，来研究本文研究的相互作用中的非加和效应。我们的结果表明，随着配位数的增加，离子与第一邻近水分子之间的相互作用能降低。我们还发现，在所研究的体系中，氢键和离子-偶极相互作用之间存在强烈的协同作用。这种协同作用极大地影响了离子与其第一和第二溶剂化壳层在水溶液中的相互作用。总的来说，我们相信本文提供了关于离子-偶极相互作用如何相互作用以及它们如何与氢键等其他相互作用在水介质中非加和效应框架内相关的有价值的信息。
