Large Angular Jump Mechanism Observed for Hydrogen Bond Exchange in Aqueous Perchlorate Solution
Large Angular Jump Mechanism Observed for Hydrogen Bond Exchange in Aqueous Perchlorate Solution
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DOI：
10.1126/science.1187707
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发表时间：
2010-05-21
期刊：
影响因子：
56.9
通讯作者：
Gaffney, K. J.
中科院分区：
文献类型：
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作者：
Ji, Minbiao;Odelius, Michael;Gaffney, K. J.
尽管进行了大量的实验和理论研究，但溶液中氢键（H-键）转换的机制仍然存在争议。我们应用偏振选择多维振动光谱研究了NaClO（4）水溶液中的氢键交换机理。结果表明，水分子通过大的、瞬时的角旋转移动其在水和高氯酸盐受体之间的捐赠氢键。使用跳跃交换动力学模型，我们提取了49 +/- 4度的平均跳跃角，与在相同的NaClO（4）水溶液的分子动力学模拟中观察到的跳跃角定性一致。
The mechanism for hydrogen bond (H-bond) switching in solution has remained subject to debate despite extensive experimental and theoretical studies. We have applied polarization-selective multidimensional vibrational spectroscopy to investigate the H-bond exchange mechanism in aqueous NaClO(4) solution. The results show that a water molecule shifts its donated H-bonds between water and perchlorate acceptors by means of large, prompt angular rotation. Using a jump-exchange kinetic model, we extracted an average jump angle of 49 +/- 4 degrees, in qualitative agreement with the jump angle observed in molecular dynamics simulations of the same aqueous NaClO(4) solution.