Specific Ion Effects on Hydrogen-Bond Rearrangements in the Halide–Dihydrate Complexes
Specific Ion Effects on Hydrogen-Bond Rearrangements in the Halide–Dihydrate Complexes
复制标题
特定离子对卤化物二水合物中氢键重排的影响
DOI：
10.1021/acs.jpclett.9b00899
复制
发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Paesani, Francesco
中科院分区：
文献类型：
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作者：
Bajaj, Pushp;Zhuang, Debbie;Paesani, Francesco
Small aqueous ionic clusters represent ideal systems to investigate the microscopic hydrogen-bonding structure and dynamics in ion hydration shells. In this context, halide–dihydrate complexes are the smallest systems where the interplay between halide–water and water–water interactions can be studied simultaneously. Here, quantum molecular dynamics simulations unravel specific ion effects on the temperature-dependent structural transition in X–(H2O)2complexes (X = Cl, Br, and I), which is induced by the breaking of the water–water hydrogen bond. A systematic analysis of the hydrogen-bonding rearrangements at low temperature provides fundamental insights into the competition between halide–water and water–water interactions depending on the properties of the halide ion. While the halide–water hydrogen-bond strength decreases going from Cl–(H2O)2to I–(H2O)2, the opposite trend in observed in the strength of the water–water hydrogen-bond, suggesting that nontrivial many-body effects may also be at play in the hydration shells of halide ions in solution, especially in frustrated systems (e.g., interfaces) where the water molecules can have dangling OH bonds.
