Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
J Am Chem Soc. 2011 Jul 13;133(27):10360-3. doi: 10.1021/ja2026695. Epub 2011 Jun 21.
Phase-sensitive vibrational sum-frequency experiments on the water surface, using isotopic mixtures of water and heavy water, have recently been performed. The experiments show a positive feature at low frequency in the imaginary part of the susceptibility, which has been difficult to interpret, and impossible to reproduce using two-body (pairwise-additive) water simulation models. We have reparameterized a new three-body simulation model for liquid water, and with this model we calculate the imaginary part of the sum-frequency susceptibility, finding good agreement with experiment for dilute HOD in D(2)O. Theoretical analysis provides a molecular-level structural interpretation of these new and exciting experiments. In particular, we do not find evidence of any special ice-like ordering at the surface of liquid water.
最近，在水表面上进行了使用重水和轻水同位素混合物的相敏振动和频实验。实验在介电常数虚部中显示出低频处的正特征，这一直难以解释，并且使用二体（加和）水模拟模型无法重现。我们重新参数化了一种新的用于液体水的三体模拟模型，并且使用该模型计算和频介电常数虚部，发现对于稀有的 HOD 在 D(2)O 中有很好的实验吻合度。理论分析为这些新的和令人兴奋的实验提供了分子水平结构解释。特别是，我们没有发现任何特殊冰状有序结构的证据存在于液态水的表面。
