PULSE Institute for Ultrafast Energy Science, SLAC National Accelerator Laboratory, Stanford University, Stanford, CA 94305, USA.
Science. 2010 May 21;328(5981):1003-5. doi: 10.1126/science.1187707.
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 NaClO4 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 NaClO4 solution.
尽管已经进行了广泛的实验和理论研究，但氢键（H-bond）在溶液中切换的机制仍然存在争议。我们应用极化选择多维振动光谱研究了水溶液中高氯酸钠溶液的氢键交换机制。结果表明，水分子通过大的、快速的角旋转将其捐赠的氢键在水和高氯酸受体之间转移。使用跳跃交换动力学模型，我们提取了平均跳跃角为 49 ± 4 度，与相同高氯酸钠水溶液的分子动力学模拟中观察到的跳跃角定性一致。
