Molecular Interaction and Orientation of HOCl on Aqueous and Ice Surfaces.
Molecular Interaction and Orientation of HOCl on Aqueous and Ice Surfaces.
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DOI：
10.1021/jacs.0c08994
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发表时间：
2020-09
影响因子：
15
通讯作者：
J. Zhong;Weina Zhang;Sijia Wu;T. An;J. S. Francisco
中科院分区：
文献类型：
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作者：
J. Zhong;Weina Zhang;Sijia Wu;T. An;J. S. Francisco
次氯酸（HOCl）在冰面上的相互作用和取向一直是人们极大的兴趣，因为它对臭氧消耗具有重要意义。由于HOCl与冰表面相互作用，以前的经典分子动力学模拟表明其OH部分定向到冰表面的外部，而在0 K下进行的量子计算表明其Cl原子暴露。为了解决这一矛盾，本文采用Born-Oppenheimer分子动力学模拟方法，模拟结果表明，在室温下，HOCl与界面水之间的相互作用主要是由（HOCl）H-O（H2O）的强氢键控制的.因此，HOCl主要充当水表面的质子供体，其因此可以通过界面水的促进而参与质子转移反应。此外，发现HOCl的Cl原子暴露于水表面的外部。因此，在HOCl在水表面的多相反应中，Cl原子成为反应位点，并且容易被其他物种攻击。
The interaction and orientation of hypochlorous acid (HOCl) on the ice surface has been of great interest as it has important implications to ozone depletion. As HOCl interacts with the ice surface, previous classical molecular dynamics simulations suggest its OH moiety orients to the outside of the ice surface, whereas the quantum calculations performed at 0 K indicate its Cl atom is exposed. To resolve this contradiction, herein, Born-Oppenheimer molecular dynamics simulations are adopted, and the results suggest that at ambient temperature, the interaction between HOCl with interfacial water is dominated by the robust H-bond of (HOCl)H-O(H2O). As a result, the HOCl mainly acts as the proton donor to the water surface, which thus can participate in proton transfer reactions via the promotion of interfacial water. Moreover, the Cl atom of HOCl is found to be exposed to the outside of the water surface. Therefore, during the heterogeneous reactions of HOCl on the water surface, the Cl atom becomes the reactive site and is easily attacked by other species.