Department of Chemistry, Columbia University, New York, New York 10027, USA.
Phys Rev Lett. 2009 Dec 4;103(23):238302. doi: 10.1103/PhysRevLett.103.238302. Epub 2009 Nov 30.
First-principles molecular dynamics calculations performed in a fully converged basis set are used to reveal new details about the mechanism of the anomalous proton-transport process in water, a fundamental question dating back over 200 years. By separating actual structural diffusion from simple rattling events, wherein a proton shuttles forth and back in a hydrogen bond, it is found that the former are driven by a concerted mechanism in which hydronium begins to accept a hydrogen bond from a donor water molecule while the proton-receiving water molecule simultaneously loses one of its acceptor hydrogen bonds. The kinetics of the process are found to be in good agreement with recent experiments.
采用完全收敛基组的第一性原理分子动力学计算揭示了关于水反常质子传输过程机制的新细节，这个问题可以追溯到 200 多年前。通过将实际的结构扩散与简单的摇晃事件（质子在氢键中来回穿梭）分离，发现前者是由协同机制驱动的，其中氢离子开始接受来自供体水分子的氢键，而质子受体水分子同时失去其一个受体氢键。该过程的动力学与最近的实验结果非常吻合。
