Like-charge ion pairs of hydronium and hydroxide in aqueous solution?
Literature Information
Manik Kumer Ghosh, Tae Hoon Choi, Cheol Ho Choi
The like-charge ion pairings of hydronium and hydroxide were investigated using both ab initio cluster calculations and QM/MM-MD aqueous simulations. While only a two-water-bridged H3O+(H2O)2H3O+ is found in hydronium cluster calculations, three clusters of HO−(H2O)2HO−, HO−(H2O)3HO− and HO−(H2O)4HO− are stable dihydroxide aggregates. In addition, an interesting yet very stable parallelogram structure of [O–H⋯H–O]2− without any bridging water was also discovered using QM/MM-MD simulations. According to our analysis, its unique structure reduces the electrostatic repulsion and allows stable coordination with solvents at the same time. In conclusion, hydroxide can form stronger like-ion pairs than hydronium in aqueous solution mostly due to its versatile coordination ability with solvents.
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.













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