Hydrated cation-π interactions of π-electrons with hydrated Mg2+ and Ca2+ cations

Hydrated cation-π interactions at liquid-solid interfaces between hydrated cations and aromatic ring structures of carbon-based materials are pivotal in many material, biological, and chemical processes, and water serves as a crucial mediator in these interactions. However, a full understanding of the hydrated cation-π interactions between hydrated alkaline earth cations and aromatic ring structures, such as graphene remains elusive. Here, we present a molecular picture of hydrated cation-π interactions for Mg2+ and Ca2+ by using the density functional theory methods. Theoretical results show that the graphene sheet can distort the hydration shell of the hydrated Ca2+ to interact with Ca2+ directly, which is water-cation-π interactions. In contrast, the hydration shell of the hydrated Mg2+ is quite stable and the graphene sheet interacts with Mg2+ indirectly, mediated by water molecules, which is the cation-water-π interactions. These results lead to the anomalous order of adsorption energies for these alkaline earth cations, with hydrated Mg2+-π < hydrated Ca2+-π when the number of water molecules is large (n ≥ 6), contrary to the order observed for cation-π interactions in the absence of water molecules (n = 0). The behavior of hydrated alkaline earth cations adsorbed on a graphene surface is mainly attributed to the competition between the cation-π interactions and hydration effects. These findings provide valuable details of the structures and the adsorption energy of hydrated alkaline earth cations adsorbed onto the graphene surface.